Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
  • C03B19/066—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction for the production of quartz or fused silica articles
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/10—Forming beads
  • C03B19/108—Forming porous, sintered or foamed beads
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/10—Forming beads
  • C03B19/1095—Thermal after-treatment of beads, e.g. tempering, crystallisation, annealing
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
  • C03C1/02—Pretreated ingredients
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/51—Particles with a specific particle size distribution
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/11—Powder tap density
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/14—Pore volume
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/80—Compositional purity
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B2201/00—Type of glass produced
  • C03B2201/02—Pure silica glass, e.g. pure fused quartz
  • C03B2201/03—Impurity concentration specified
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B2201/00—Type of glass produced
  • C03B2201/02—Pure silica glass, e.g. pure fused quartz
  • C03B2201/03—Impurity concentration specified
  • C03B2201/04—Hydroxyl ion (OH)
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2201/00—Glass compositions
  • C03C2201/06—Doped silica-based glasses
  • C03C2201/08—Doped silica-based glasses containing boron or halide
  • C03C2201/11—Doped silica-based glasses containing boron or halide containing chlorine
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2201/00—Glass compositions
  • C03C2201/06—Doped silica-based glasses
  • C03C2201/20—Doped silica-based glasses containing non-metals other than boron or halide
  • C03C2201/23—Doped silica-based glasses containing non-metals other than boron or halide containing hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2201/00—Glass compositions
  • C03C2201/06—Doped silica-based glasses
  • C03C2201/30—Doped silica-based glasses containing metals
  • C03C2201/32—Doped silica-based glasses containing metals containing aluminium
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2203/00—Production processes
  • C03C2203/10—Melting processes
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
  • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
  • G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
  • G01N21/412—Index profiling of optical fibres
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P40/00—Technologies relating to the processing of minerals
  • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
  • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

• the invention relates to a method for producing a quartz glass body comprising the method steps i.) Providing a silicon dioxide granulate from a fumed silica powder, ii.) Forming a glass melt from the silicon dioxide granules, and iii) forming a quartz glass body from at least a part of the glass melt, wherein the quartz glass body OH content of less than 10 ppm, a chlorine content of less than 60 ppm and an aluminum content of less than 200 ppb.
• the invention further relates to a quartz glass body obtainable by this method.
• the invention relates to a molded body and a structure, which are each obtainable by further processing of the quartz glass body. Background of the invention
• Quartz glass, quartz glass products and products containing quartz glass are known.
• various methods for producing quartz glass and quartz glass bodies are already known. Nevertheless, considerable efforts continue to be made to identify manufacturing processes by which silica glass of even higher purity, that is, absence of impurities, can be produced.
• quartz glass and its processing products particularly high demands, for example, in terms of homogeneity and purity. This is, among other things, the case with quartz glass, which is used in production steps in semiconductor manufacturing.
• any contamination of the glass body potentially leads to defects of the semiconductor, and thus to rejects in the production.
• the high-purity quartz glass used for these methods are therefore produced very expensive. They are high priced.
• Known methods for producing quartz glass bodies involve melting silica and forming into melted quartz glass bodies. Irregularities in a vitreous body, for example due to the inclusion of gases in the form of bubbles, can result in failure of the vitreous under load, especially at high temperatures, or preclude use for a particular purpose. Thus, impurities of the quartz glass-forming raw material can lead to the formation of cracks, bubbles, streaks and discoloration in the quartz glass. Impurities can also be worked out in the glass body and transferred to the treated semiconductor components. This is the case, for example, in etching processes and then leads to rejects in the semiconductor blanks. A frequently occurring problem in the known production methods is consequently an insufficient quality of the quartz glass body. Another aspect concerns the raw material efficiency.
• An object of the present invention is to at least partially overcome one or more of the disadvantages of the prior art.
• components is meant in particular components that can be used for or in reactors for chemical and / or physical treatment steps.
• treatment steps are plasma etching, chemical etching and plasma doping.
• Foreign atoms are understood to mean components that have not been deliberately introduced.
• Homogeneity of a property or a substance is a measure of the uniformity of the distribution of that property or substance in a sample.
• the material homogeneity is a measure of the uniformity of the distribution of elements and compounds contained in the component, in particular OH, chlorine, metals, in particular aluminum, alkaline earth metals, refractory metals and dopants.
• Another object is to provide a method by which a silicon dioxide material for components can be produced in a cost and time saving manner.
• Silica material for components can be produced.
• Another object is to further improve the processability of components.
• Another task is to further improve the assembly of components.
• a method for producing a quartz glass body comprising pyrogenic silicon dioxide comprising the following method steps:
• the silica powder has the following properties:
• silica granules have a larger particle diameter than the silica powder
• quartz glass body has the following properties:
• C] has an aluminum content of less than 200 ppb
• ppb and ppm are each based on the total weight of the quartz glass body.
• Amorphous means that the silica powder is preferably in the form of amorphous silica particles.
• the temperature T T is in a range of 1000 to 1700 ° C;
• the period t T is in a range of 1 to 6 hours.
• the cooling is carried out in a temperature range of 1300 to 1000 ° C at a rate of not more than 1 K / min.
• the quartz glass body is characterized by at least one of the following features:
• K] has a refractive index homogeneity of less than 1x10 " *;
• ppb and ppm are each based on the total weight of the quartz glass body.
• the silicon dioxide powder has at least one of the following features:
• f. a total content of metals other than aluminum of less than 5 ppm;
• G. at least 70% by weight of the powder particles have a primary particle size in a range of 10 to 100 nm;
• H a tamped density in a range of 0.001 to 0.3 g / cm 3 ;
• ppm and ppb are each related to the total mass of the silica powder.
• the method of any one of the preceding embodiments, wherein processing the silica powder into a silica granule comprises the steps of:
• G an average particle size in a range of 50 to 500 ⁇ ;
• ppm and ppb are each based on the total weight of the silica granules II.
• a quartz glass body containing fumed silica, the fused silica body having the following properties:
• C] has an aluminum content of less than 200 ppb
• ppb and ppm are each based on the total weight of the quartz glass body.
• K] has a refractive index homogeneity of less than 1x10 " *;
• ppb and ppm are each based on the total weight of the quartz glass body.
• a method for producing a shaped body comprising the following method steps:
• a molded article obtainable by a method according to embodiment 117.
• a method for producing a structure comprising the following method steps:
• silica powder into a silica granule I, the silica granules I having a larger particle diameter than the silica powder;
• Quartz glass body has the following properties:
• C] has an aluminum content of less than 200 ppb
• ppb and ppm are each based on the total weight of the quartz glass body.
• range indications also include the values called limits.
• An indication of the kind "in the range of X to Y" with respect to a size A thus means that A can take the values X, Y and values between X and Y.
• One-sided bounded areas of the kind "up to Y" for one size correspondingly, A means values Y and less than Y.
• a first subject of the present invention is a method for producing a quartz glass body comprising pyrogenic silicon dioxide, comprising the following method steps:
• silica granules have a larger particle diameter than the silica powder
• quartz glass body has the following properties:
• C] has an aluminum content of less than 200 ppb
• the provision of the silicon dioxide granules includes the following method steps:
• silica powder into a silica granule, the silica granule having a larger particle diameter than the silica powder.
• a powder is understood as meaning particles of dry solids having a primary particle size in the range of 1 to less than 100 nm.
• the silica granules can be obtained by granulating silica powder.
• a silica granule typically has a BET surface area of 3 m 2 / g or more and a density of less than 1.5 g / cm 3 .
• Granulating is understood as meaning the transfer of powder particles into granules.
• Granulation forms aggregates of multiple silica powder particles, ie larger agglomerates called “silica granules.” These are often referred to as “silica granule particles” or “granule particles.” Granules form granules in their entirety, eg, the silica granules are “silica granules.” , The silica granules have a larger particle diameter than the silica powder.
• silicon dioxide granulation is understood as meaning silicon dioxide particles obtainable by comminuting a silicon dioxide body, in particular a quartz glass body.
• a silica grain usually has a density of more than 1.2 g / cm 3 , for example in a range of 1.2 to 2.2 g / cm 3 , and more preferably about 2.2 g / cm 3 , More preferably, the BET surface area of a silica grain is generally less than 1 m 2 / g, determined according to DIN ISO 9277: 2014-01.
• silica particles suitable to the person skilled in the art come into consideration as silica particles.
• silica granules and silica granules are selected.
• silica powder namely pyrogenic silica powder
• the silica powder may be any silica powder having at least two particles. Any method which is familiar to the person skilled in the art and suitable for the present purpose can be considered as the production method. According to a preferred embodiment of the present invention, the silica powder is produced in the production of quartz glass as a by-product, in particular in the production of so-called soot bodies. Silica of such origin is often referred to as "soot dust".
• a preferred source of the silica powder is silica particles obtained in the synthetic production of soot bodies using flame hydrolysis burners.
• a rotating carrier tube which has a cylinder jacket surface, is reversibly moved back and forth along a row of burners.
• the Flammhydrolysebrennern can be supplied as fuel gases each oxygen and hydrogen and the starting materials for the formation of Siliziumdioxidprimä articles.
• the Siliziumdioxidprimä article preferably have a primary particle size of up to 100 nm.
• the silica prima particles are recognizable in their shape by scanning electron microscopy and the primary particle size can be determined.
• a portion of the silicon dioxide particles are deposited on the cylinder jacket surface of the support tube rotating about its longitudinal axis. So layer by layer of 8 ⁇ is built.
• Another part of the silica particles is not deposited on the cylinder jacket surface of the support tube, but accumulates as dust, e.g. in a filter system.
• the part of silicon dioxide particles deposited on the carrier tube is larger than the part of silica particles resulting from soot dust in the context of 8o106 0 ⁇ 6 ⁇ 8 ⁇ , based on the total weight of the silicon dioxide particles.
• soot dust is usually disposed of consuming and expensive as waste or spent without added value as a filler, e.g. in road construction, as additives in the dyestuff industry, as a raw material for tile production and for the production of hexafluorosilicic acid, which is used for the renovation of building foundations.
• a filler e.g. in road construction, as additives in the dyestuff industry, as a raw material for tile production and for the production of hexafluorosilicic acid, which is used for the renovation of building foundations.
• it is suitable as a starting material and can be processed to a high quality product.
• Fumed silica is usually in the form of amorphous silica priming particles or silica particles.
• the silica powder can be prepared by flame hydrolysis from a gas mixture.
• the silica particles are also formed in the flame hydrolysis and discharged as silica powder before agglomerates or aggregates are formed.
• the silica powder previously referred to as soot dust main product.
• starting materials for the formation of the silica powder are preferably siloxanes, silicon alkoxides and inorganic silicon compounds.
• Siloxanes are understood as meaning linear and cyclic polyalkylsiloxanes.
• Polyalkylsiloxanes preferably have the general formula
• p is an integer of at least 2, preferably from 2 to 10, more preferably from 3 to 5, and
• R is an alkyl group having 1 to 8 C atoms, preferably having 1 to 4 C atoms, more preferably one
• siloxanes selected from the group consisting of hexamethyldisiloxane, hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) or a combination of two or more thereof.
• D3 hexamethylcyclotrisiloxane
• D4 octamethylcyclotetrasiloxane
• D5 decamethylcyclopentasiloxane
• Preferred silicon alkoxides are tetramethoxysilane and methyltrimethoxysilane.
• Preferred inorganic silicon compounds as the starting material for silica powder are silicon halides, silicates, silicon carbide and silicon nitride. Particularly preferred as the inorganic silicon compound as a starting material for silica powder are silicon tetrachloride and trichlorosilane.
• the silicon dioxide powder can be prepared from a compound selected from the group consisting of siloxanes, silicon alkoxides and silicon halides.
• the silica powder can be prepared from a compound selected from the group consisting of hexamethyldisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and
• Decamethylcyclopentasiloxane tetramethoxysilane and methyltrimethoxysilane, silicon tetrachloride and trichlorosilane, or a combination of two or more thereof, for example, silicon tetrachloride and octamethylcyclotetrasiloxane, most preferably octamethylcyclotetrasiloxane.
• a preferred composition of a suitable gas mixture includes a proportion of oxygen in the flame hydrolysis in a range of 25 to 40% by volume.
• the proportion of hydrogen may be in a range of 45 to 60% by volume.
• the proportion of silicon tetrachloride is preferably from 5 to 30% by volume, all of the abovementioned% by volume, based on the total volume of the gas stream.
• the flame in the flame hydrolysis preferably has a temperature in a range from 1500 to 2500 ° C., for example in a range from 1600 to 2400 ° C., particularly preferably in one range from 1700 to 2300 ° C.
• the silica particles formed in the flame hydrolysis are removed as silica powder before agglomerates or aggregates are formed.
• the silica powder has at least one, for example at least two or at least three or at least four, more preferably at least five of the following characteristics:
• a BET surface area in a range from 20 to 60 m 2 / g, for example from 25 to 55 m 2 / g, or from 30 to 50 m 2 / g, particularly preferably from 20 to 40 m 2 / g,
• a total content of metals other than aluminum of less than 5 ppm, for example less than 2 ppm, more preferably in a range of from 1 ppb to 1 ppm;
• G. at least 70% by weight of the powder particles have a primary particle size in a range of 10 to less than 100 nm, for example in the range of 15 to less than 100 nm, more preferably in the range of 20 to less than 100 nm;
• H. a tamped density in a range of 0.001 to 0.3 g / cm 3 for example in the range of 0.002 to 0.2 g / cm 3 or from 0.005 to 0.1 g / cm 3 , preferably in the range of 0.01 to 0.06 g / cm 3 , also preferably in the range of 0.1 to 0.2 g / cm 3 , or in the range of 0.15 to 0.2 g / cm 3 ; i. a residual moisture of less than 5 wt .-%, for example in the range of 0.25 to 3 wt .-%, particularly preferably in the range of 0.5 to 2 wt .-%;
• a particle size distribution D 10 in the range of 1 to 7 ⁇ , for example in the range of 2 to 6 ⁇ or in the range of 3 to 5 ⁇ , more preferably in the range of 3.5 to 4.5 ⁇ ;
• a particle size distribution D 90 in the range of 10 to 40 ⁇ , for example in the range of 15 to 35 ⁇ , particularly preferably in the range of 20 to 30 ⁇ ;
• the silica powder contains silica.
• the silica powder contains silica in an amount of more than 95% by weight, for example, in an amount of more than 98% by weight. or more than 99% by weight or more than 99.9% by weight, based in each case on the total weight of the silicon dioxide powder. More preferably, the silica powder contains silica in an amount of more than 99.99% by weight based on the total weight of the silica powder.
• the silica powder has a metal content of metals other than aluminum of less than 5 ppm, for example less than 2 ppm, more preferably less than 1 ppm, each based on the total weight of the silica powder.
• the silica powder has a content of metals other than aluminum in an amount of at least 1 ppb.
• metals include sodium, lithium, potassium, magnesium, calcium, strontium, germanium, copper, molybdenum, tungsten, titanium, iron and chromium. These may be present, for example, as an element, as an ion, or as part of a molecule or an ion or a complex.
• the silica powder has a total content of other ingredients of less than 30 ppm, for example less than 20 ppm, more preferably less than 15 ppm, the ppm each based on the total weight of the silica powder. Often, however, the silica powder has a content of other ingredients in an amount of at least 1 ppb. Further constituents are understood as meaning all constituents of the silica powder which do not belong to the following group: silicon dioxide, chlorine, aluminum, OH groups.
• the indication of an ingredient when the ingredient is a chemical element means that it may be present as an element or as an ion in a compound or a salt.
• aluminum also includes aluminum salts, aluminum oxides and aluminum metal complexes
• chlorine includes, in addition to elemental chlorine, chlorides such as sodium chloride and hydrogen chloride. Often, the other ingredients are in the same state of matter as the substance in which they are contained.
• the indication of an ingredient when the ingredient is a chemical compound or a functional group, means that the ingredient may be in said form, as a charged chemical compound, or as a derivative of the chemical compound.
• the indication of the chemical ethanol includes ethanol as well as ethanol, for example, sodium ethanolate.
• the term “OH group” also includes silanol, water and metal hydroxides
• the term derivative in acetic acid also includes acetic acid ester and acetic anhydride
• at least 70% of the powder particles of the silica powder have a primary particle size of less than, based on the number of powder particles 100 nm, for example in the range from 10 to 100 nm or from 15 to 100 nm, and particularly preferably in the range from 20 to 100 nm
• the primary particle size is determined by dynamic light scattering in accordance with ISO 13320: 2009-10 75% of the powder particles of the silica powder, based on the number of powder particles, a primary particle size of less than 100 nm, for example in the range of 10 to 100 nm or from 15 to 100 nm, and particularly preferably in the range of 20 to 100 nm
• at least 80% of the powder particles of the silica powder, based on the number of powder particles have a primary article size of less than 100 nm
• At least 85% of the powder particles of the silica powder have a primary article size of less than 100 nm, for example in the range of 10 to 100 nm or of 15 to 100 nm, and more preferably in the range of 20 up to 100 nm.
• At least 90% of the powder particles of the silica powder have a primary article size of less than 100 nm, for example in the range of 10 to 100 nm or of 15 to 100 nm, and particularly preferably in the region of 20 up to 100 nm.
• At least 95% of the powder particles of the silica powder have a primary article size of less than 100 nm, for example in the range of 10 to 100 nm or 15 to 100 nm, and more preferably in the range of 20 up to 100 nm.
• the silica powder has a particle size Di 0 in the range of 1 to 7 ⁇ , for example in the range of 2 to 6 ⁇ or in the range of 3 to 5 ⁇ , particularly preferably in the range of 3.5 to 4.5 ⁇ .
• the silica powder has a particle size D 50 in the range of 6 to 15 ⁇ , for example in the range of 7 to 13 ⁇ or in the range of 8 to 1 1 ⁇ , more preferably in the range of 8.5 to 10.5 ⁇ .
• the silica powder has a particle size D 90 in the range of 10 to 40 ⁇ , for example in the range of 15 to 35 ⁇ , more preferably in the range of 20 to 30 ⁇ .
• the silica powder has a specific surface area (BET surface area) in a range from 20 to 60 m 2 / g, for example from 25 to 55 m 2 / g, or from 30 to 50 m 2 / g, particularly preferably from 20 up to 40 m 2 / g.
• BET surface area is determined according to the method of Brunauer, Emmet and Teller (BET) on the basis of DIN 66132 and is based on gas absorption at the surface to be measured.
• the silica powder has a pH of less than 7, for example in the range from 3 to 6.5 or from 3.5 to 6 or from 4 to 5.5, more preferably in the range from 4.5 to 5.
• Der pH value can be determined by means of a stick-in electrode (4% silicon dioxide powder in water).
• the silicon dioxide powder preferably has the feature combination a./b./c. or a./b./f. or a./b./g. on, more preferably the combination of features a./b./c./f. or a./b./c./g. or a./b./f./g., particularly preferably the combination of features a./b./c./f./g.
• the silicon dioxide powder preferably has the feature combination a./b./c. wherein the BET surface area is in a range of 20 to 40 m 2 / g, the bulk density is in a range of 0.05 to 0.3 g / ml, and the carbon content is less than 40 ppm.
• the silicon dioxide powder preferably has the feature combination a./b./f. wherein the BET surface area is in a range of 20 to 40 m 2 / g, the bulk density in a range of 0.05 to 0.3 g / ml, and the total content of metals other than aluminum are within a range from 1 ppb to 1 ppm.
• the silicon dioxide powder preferably has the feature combination a./b./g.
• the BET surface area is in a range of 20 to 40 m 2 / g
• the bulk density is in a range of 0.05 to 0.3 g / ml
• at least 70 wt% of the powder particles have a primary particle size in one Range from 20 to less than 100 nm.
• the silicon dioxide powder more preferably has the feature combination a./b./c./f. wherein the BET surface area is in a range of 20 to 40 m 2 / g, the bulk density is in a range of 0.05 to 0.3 g / ml, the carbon content is less than 40 ppm, and the total content of metals , which are different from aluminum, is in a range of 1 ppb to 1 ppm.
• the silicon dioxide powder more preferably has the feature combination a./b./c./g. wherein the BET surface area is in a range of 20 to 40 m 2 / g, the bulk density is in a range of 0.05 to 0.3 g / ml, the carbon content is less than 40 ppm and at least 70 wt. -% of the powder particles have a Primä article size in a range of 20 to less than 100 nm.
• the silicon dioxide powder more preferably has the feature combination a./b./f./g.
• the BET surface area is in a range of 20 to 40 m 2 / g
• the bulk density is in a range of 0.05 to 0.3 g / ml
• the total content of metals other than aluminum in a range of from 1 ppb to 1 ppm and at least 70% by weight of the powder particles have a primary particle size in a range of 20 to less than 100 nm.
• the silicon dioxide powder particularly preferably has the feature combination a./b./c./f./g. wherein the BET surface area is in a range of 20 to 40 m 2 / g, the bulk density is in a range of 0.05 to 0.3 g / ml, the carbon content is less than 40 ppm, the total content of metals which are different from aluminum, is in a range of 1 ppb to 1 ppm, and at least 70% by weight of the powder particles have a primary particle size in a range of 20 to less than 100 nm.
• the silicon dioxide powder is processed in step II to a granular silica, wherein the silica granules having a larger particle diameter than the silica powder.
• Suitable in principle are all methods known to those skilled in the art, which lead to an increase in the particle diameter.
• the silica granules have a particle diameter larger than the particle diameter of the silica powder.
• the particle diameter of the silica granules is in a range of 500 to 50,000 times larger than the particle diameter of the silica powder, for example, 1,000 to 10,000 times larger, more preferably 2,000 to 8,000 times larger.
• At least 90% of the silicon dioxide granules provided in step i) are preferably formed from pyrogenically produced silicon dioxide powder, for example at least 95% by weight or at least 98% by weight, more preferably at least 99% by weight or more, based in each case on the Total weight of silica granules.
• the silica granules used have the following features:
• G an average particle size in a range of 50 to 500 ⁇ ;
• ppm and ppb are each based on the total weight of the silica granules.
• the granules of the silica granules preferably have a spherical morphology.
• Spherical morphology refers to a round to oval shape of the particles.
• the granules of the silica granules preferably have an average sphericity in a range of 0.7 to 1.3 SPHT3, for example, an average sphericity in a range of 0.8 to 1.2 SPHT3, more preferably an average sphericity in a range of 0 , 85 to 1.1 SPHT3 on.
• the characteristic SPHT3 is described in the test methods.
• the granules of the silica granules have an average symmetry in a range of 0.7 to 1.3 Symm3, for example a mean symmetry in a range of 0.8 to 1.2 Symm3, more preferably has a mean symmetry in a range of 0.85 to 1.1 Symm3.
• Symm3 The feature of symmetry Symm3 is described in the test methods.
• the silica granules have a metal content of metals other than aluminum of less than 1000 ppb, for example less than 500 ppb, more preferably less than 100 ppb, each based on the total weight of the silica granules. Often, however, the silica granules have a content of metals other than aluminum in an amount of at least 1 ppb.
• the silica granules have a metal content of metals other than aluminum of less than 1 ppm, preferably in a range of 40 to 900 ppb, for example in a range of 50 to 700 ppb, more preferably in a range of 60 to 500 ppb, respectively based on the total weight of the silica granules.
• metals include sodium, lithium, potassium, magnesium, calcium, strontium, germanium, copper, molybdenum, titanium, iron and chromium. These may be present, for example, as an element, as an ion, or as part of a molecule or an ion or a complex.
• the silica granules may contain further constituents, for example in the form of molecules, ions or elements.
• the silica granules contain less than 500 ppm, for example less than 300 ppm, more preferably less than 100 ppm, in each case based on the total weight of the silica granules, further constituents.
• further ingredients are included in an amount of at least 1 ppb.
• the further constituents may in particular be selected from the group consisting of carbon, fluoride, iodide, bromide, phosphorus or a mixture of at least two thereof.
• the silica granules contain less than 10 ppm carbon, for example less than 8 ppm or less than 5 ppm, more preferably less than 4 ppm, each based on the total weight of the silica granules. Often, carbon in an amount of at least 1 ppb is contained in the silica granules.
• the silica granules contain less than 100 ppm, for example less than 80 ppm, more preferably less than 70 ppm, based in each case on the total weight of the silica granules, of further constituents. Often, however, the other ingredients are included in an amount of at least 1 ppb.
• step II includes the following steps:
• a liquid is understood to be a substance or a mixture of substances which is liquid at a pressure of 1013 hPa and a temperature of 20 ° C.
• a "slurry" in the sense of the present invention means a mixture of at least two substances, wherein the mixture has at least one liquid and at least one solid under the conditions under consideration.
• Suitable liquids are, in principle, all those known to those skilled in the art and suitable for the present purpose Substances and Mixtures
• the liquid is selected from the group consisting of organic liquids and water
• the silica powder in the liquid is in an amount of less than 0.5 g / L, preferably in an amount of less than 0.25 g / L, more preferably in an amount of less than 0.1 g / L soluble, the g / L each expressed as g of silica powder per liter of liquid.
• Preferred liquids are polar solvents. These can be organic liquids or water.
• the liquid is preferably selected from the group consisting of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and mixtures of more than one thereof.
• the liquid is water.
• the liquid includes distilled or deionized water.
• the silica powder is processed into a slurry.
• the silica powder is almost insoluble in the liquid at room temperature, but may be incorporated into the liquid in high weight fractions to obtain the slurry.
• the silica powder and the liquid may be mixed in any manner.
• the silica powder may be added to the liquid or the liquid to the silica powder.
• the mixture may be agitated during addition or after addition. Most preferably, the mixture is agitated during and after adding. Examples of agitation are shaking and stirring, or a combination of both.
• the silica powder may be added to the liquid with stirring. More preferably, a portion of the silica powder may be added to the liquid, with the mixture thus obtained being agitated, and the mixture subsequently mixed with the remainder of the silica powder.
• a portion of the liquid may be added to the silica powder, the mixture thus obtained being agitated, and the mixture subsequently mixed with the remainder of the liquid.
• the slurry is a suspension in which the silica powder is evenly distributed in the liquid.
• uniformly it is meant that the density and composition of the slurry at each point does not differ by more than 10% from the average density and the average composition, each based on the total amount of slurry
• a uniform distribution of the silica powder in the liquid can be made or obtained by moving as previously described, or both.
• the slurry has a liter weight in the range of 1000 to 2000 g / L, for example in the range of 1200 to 1900 g / L or of 1300 to 1800 g / L, more preferably in the range of 1400 to 1700 g / L.
• the weight per liter is determined by weighing a volume calibrated container.
• the slurry has at least one, for example at least two or at least three or at least four, more preferably at least five of the following characteristics:
• the slurry has a temperature of more than 0 ° C, preferably in a range of 5 to 35 ° C;
• the slurry has a zeta potential at a pH of 7 in a range of 0 to -100 mA, for example from -20 to -60 mA, more preferably from -30 to -45 mA;
• the slurry has a pH in a range of 7 or more, for example greater than 7 or a pH in the range of 7.5 to 13 or from 8 to 11, more preferably from 8.5 to 10 ;
• the slurry has an isoelectric point of less than 7, for example in one
• the slurry has a solids content of at least 40% by weight, for example in one
• the slurry has a viscosity in accordance with DIN 53019-1 (5 rpm, 30 wt .-%) in a range of 500 to 2000 mPas, for example in the range of 600 to 1700 mPas, particularly preferably in the range of 1000 to 1600 mPas ;
• the slurry has a thixotropy according to DIN SPEC 91143-2 (30 wt .-% in water, 23 ° C,
• the silica particles in the slurry have in a 4% by weight slurry an average particle size in suspension according to DIN ISO 13320-1 in the range from 100 to 500 nm, for example in a range from 200 to 300 nm.
• the silica particles in a 4 wt .-% aqueous slurry has a particle size D 10 in a range of 50 to 250 nm, more preferably in the range of 100 to 150 nm.
• the silica particles in a 4 wt .-% aqueous slurry has a particle size D 50 in the range of 100 to 400 nm, more preferably in the range of 200 to 250 nm.
• the silica particles have, in a 4 wt .-% aqueous slurry has a particle size D 90 in the range of 200 to 600 nm, more preferably in a range of 350 to 400 nm.
• the particle size is determined by means of DIN ISO 13320-1.
• the "isolectric point" is the pH at which the zeta potential assumes the value 0.
• the zeta potential is determined in accordance with ISO 13099-2: 2012
• substances such as NaOH or NH 3 , for example as an aqueous solution of the slurry, may be added, often causing the slurry to agitate.
• the silica granules are obtained by granulating silica powder.
• Granulating is understood as meaning the transfer of powder particles into granules.
• aggregates of multiple silica powder particles form larger agglomerates, referred to as “silica granules.” These are often referred to as “silica particles,” “silica granule particles,” or “granule particles.”
• granules form granules, e.g. the silica granules a "silica granules”.
• any granulation process which is known to the person skilled in the art and suitable for granulating silicon dioxide powder can be selected.
• the granulation process a distinction can be made between built-up granulation and pressing granulation, and further between wet and dry granulation processes.
• Known methods are rolling granulation in a granulating dish, spray granulation, centrifugal atomization, fluidized-bed granulation, granulation processes using a granulating mill, compaction, roll pressing, briquetting, flake production or extrusion.
• a silica granule is obtained by spray granulating the slurry.
• Spray granulation is also referred to as spray drying.
• the spray drying is preferably carried out in a spray tower.
• the slurry is pressurized at elevated temperature.
• the pressurized slurry is then released through a nozzle and sprayed into the spray tower.
• droplets form, which dry instantly and initially form dry micro-particles ("germs.")
• the micro-particles together with a gas stream acting on the particles, form a fluidized bed which holds them in suspension and can thus form a surface for drying further droplets form.
• the nozzle through which the slurry is sprayed into the spray tower preferably forms an inlet into the interior of the spray tower.
• the nozzle preferably has a contact surface with the slurry during spraying.
• contact area is meant the area of the nozzle which in contact with the slurry during spraying comes.
• at least a portion of the nozzle is shaped as a tube through which the slurry is passed during spraying so that the inside of the hollow tube comes in contact with the slurry.
• the contact surface preferably includes a glass, a plastic or a combination thereof.
• the contact surface comprises a glass, more preferably quartz glass.
• the contact surface includes a plastic.
• all plastics known to those skilled in the art are suitable, which are stable at the process temperatures and do not release any foreign atoms to the slurry.
• Preferred plastics are polyolefins, for example homo- or copolymers containing at least one olefin, more preferably homopolymers or copolymers comprising polypropylene, polyethylene, polybutadiene or combinations of two or more thereof.
• the contact surface consists of a glass, a plastic or a combination thereof, for example selected from the group consisting of quartz glass and polyolefins, more preferably selected from the group consisting of quartz glass and homopolymers or copolymers comprising polypropylene, polyethylene, polybutadiene or combinations of two or more of them.
• the contact surface preferably contains no metals, in particular no tungsten, titanium, tantalum, chromium, cobalt, nickel, iron, vanadium, zirconium and manganese.
• the contact surface and the other parts of the nozzle consist of the same or of different materials.
• the other parts of the nozzle contain the same material as the contact surface.
• the other parts of the nozzle contain a different material from the contact surface.
• the contact surface may be coated with a suitable material, for example a glass or a plastic.
• the nozzle is preferably more than 70% by weight, based on the total weight of the nozzle, of an element selected from the group consisting of glass, plastic or a combination of glass and plastic, for example more than 75% by weight. % or more than 80 wt .-% or more than 85 wt .-% or more than 90 wt .-% or more than 95 wt .-%, particularly preferably more than 99 wt .-%.
• the nozzle comprises a nozzle plate.
• the nozzle plate is preferably formed of glass, plastic or a combination of glass and plastic.
• the nozzle plate is formed of glass, particularly preferably quartz glass.
• the nozzle plate is formed of plastic.
• Preferred plastics are polyolefins, for example homo- or copolymers containing at least one olefin, more preferably homopolymers or copolymers comprising polypropylene, polyethylene, polybutadiene or combinations of two or more thereof.
• the nozzle plate preferably contains no metals, in particular no tungsten, titanium, tantalum, chromium, cobalt, nickel, iron, vanadium, zirconium and manganese.
• the nozzle preferably comprises a spiral screw.
• the spiral screw is preferably made of glass, plastic or a combination of glass and plastic.
• the spiral screw is formed of glass, more preferably quartz glass.
• the spiral screw is formed from plastic.
• Preferred plastics are polyolefins, for example homopolymers or copolymers containing at least one olefin, more preferably homopolymers or copolymers comprising polypropylene, polyethylene, polybutadiene or combinations of two or more of it.
• the spiral screw contains no metals, in particular no tungsten, titanium, tantalum, chromium, cobalt, nickel, iron, vanadium, zirconium and manganese.
• the nozzle may further comprise other components.
• Preferred further components are a nozzle body, particularly preferred is a nozzle body surrounding the spiral screw and the nozzle plate, a cross piece and a baffle plate.
• a nozzle preferably comprises one or more, particularly preferably all, of the further components.
• the other components can, independently of one another, in principle consist of any material known to the person skilled in the art and suitable for this purpose, for example of a metal-containing material, of glass or of a plastic.
• the nozzle body is formed of glass, more preferably quartz glass.
• the other components are formed from plastic.
• Preferred plastics are polyolefins, for example homopolymers or copolymers containing at least one olefin, more preferably homopolymers or copolymers comprising polypropylene, polyethylene, polybutadiene or combinations of two or more thereof.
• the other components preferably do not contain any metals, in particular no tungsten, titanium, tantalum, chromium, cobalt, nickel, iron, vanadium, zirconium and manganese.
• the spray tower has a gas inlet and a gas outlet.
• gas inlet gas can be introduced into the interior of the spray tower, and through the gas outlet, it can be discharged. It is also possible to introduce gas through the nozzle into the spray tower. Similarly, gas can be discharged through the outlet of the spray tower. Further preferably, gas may be supplied via the nozzle and a gas inlet of the spray tower, and discharged via the outlet of the spray tower and a gas outlet of the spray tower.
• an atmosphere selected from air, an inert gas, at least two inert gases or a combination of air with at least one inert gas, preferably at least two inert gases, is present in the interior of the spray tower.
• inert gases are preferably selected from the list consisting of nitrogen, helium, neon, argon, krypton and xenon.
• air, nitrogen or argon is present in the interior of the spray tower, more preferably air.
• the atmosphere present in the spray tower is part of a gas stream.
• the gas stream is preferably introduced into the spray tower via a gas inlet and discharged via a gas outlet. It is also possible to introduce parts of the gas stream through the nozzle and divert parts of the gas stream through a solids outlet.
• the gas stream can take up additional components in the spray tower. These may originate from the slurry during spray drying and pass into the gas stream.
• a dry gas stream is fed to the spray tower.
• a dry gas stream is understood as meaning a gas or a gas mixture whose relative humidity is below the condensation point at the temperature set in the spray tower.
• a relative humidity of 100% corresponds to a water volume of 17.5 g / m 3 at 20 ° C.
• the gas is preferably preheated to a temperature in a range of from 150 to 450 ° C, for example from 200 to 420 ° C or from 300 to 400 ° C, more preferably from 350 to 400 ° C.
• the interior of the spray tower is preferably tempered.
• the temperature in the interior of the spray tower is up to 550 ° C, for example 300 to 500 ° C, more preferably 350 to 450 ° C.
• the gas stream at the gas inlet preferably has a temperature in a range from 150 to 450 ° C, for example from 200 to 420 ° C or from 300 to 400 ° C, particularly preferably from 350 to 400 ° C.
• the withdrawn gas stream preferably has a temperature of less than 170 ° C, for example from 50 to 150 ° C, more preferably from 100 to 130 ° C. More preferably, the difference between the temperature of the gas stream at the time of introduction and the gas flow when discharged is in a range of 100 to 330 ° C, for example, 150 to 300 ° C.
• the silica granules thus obtained are present as an agglomerate of individual particles of silica powder.
• the individual particles of the silicon dioxide powder are still recognizable in the agglomerate.
• the average particle size of the particles of the silica powder is preferably in the range of 10 to 1000 nm, for example, in the range of 20 to 500 nm or 30 to 250 nm or 35 to 200 nm or 40 to 150 nm, or more preferably in the range from 50 to 100 nm.
• the average particle size of these particles is determined according to DIN ISO 13320-1.
• the spray drying can be carried out in the presence of auxiliaries. In principle, all substances can be used as auxiliaries, which are known in the art and appear suitable for the present purpose.
• Suitable auxiliaries are, for example, so-called binders.
• suitable binders are metal oxides such as calcium oxide, metal carbonates such as calcium carbonate and polysaccharides such as cellulose, cellulose ethers, starch and starch derivatives.
• spray drying is particularly preferably carried out without auxiliaries.
• a portion thereof is separated.
• the separation is done by sifting or sieving.
• the sifting is preferably carried out by a cyclone, which is preferably arranged in the lower region of the spray tower, particularly preferably above the outlet of the spray tower.
• particles having a particle size of more than 1000 ⁇ m, for example having a particle size of more than 700 ⁇ m, are particularly preferred preferably separated by sieving with a particle size of more than 500 ⁇ .
• the sieving of the particles can be carried out in principle by all methods known to the person skilled in the art and suitable for this purpose. Sieving is preferably carried out by means of a vibrating trough.
• the spray-drying of the slurry through a nozzle into a spray tower is characterized by at least one, for example two or three, most preferably all of the following features:
• a temperature of the droplets entering the spray tower in a range of 10 to 50 ° C, preferably in a range of 15 to 30 ° C, more preferably in a range of 18 to 25 ° C.
• a temperature at the spray tower side of the nozzle in a range of 100 to 450 ° C, for example in a range of 250 to 440 ° C, more preferably from 350 to 430 ° C;
• a slurry throughput through the die in a range of 0.05 to 1 m 3 / h, for example in a range of 0.1 to 0.7 m 3 / h or from 0.2 to 0.5 m 3 / h, more preferably in a range of 0.25 to 0.4 m 3 / h;
• fj has a solids content of the slurry of at least 40% by weight, for example in a range of 50 to 80% by weight, or in a range of 55 to 75% by weight, particularly preferably in a range of 60 to 70% by weight .-%, in each case based on the total weight of the slurry; g] a gas flow in the spray tower in a range of 10 to 100 kg / min, for example in a range of 20 to 80 kg / min or from 30 to 70 kg / min, more preferably in a range of 40 to 60 kg / min;
• h a temperature of the gas stream entering the spray tower in a range of 100 to 450 ° C, for example in a range of 250 to 440 ° C, more preferably 350 to 430 ° C;
• the gas is selected from the group consisting of air, nitrogen and helium, or a combination of two or more thereof; preferably air;
• m at least 50 wt .-% of the spray granules, based on the total weight of the resulting during spray drying silica granules, sets a flight distance of more than 20 m, for example, more than 30 or more than 50 or more than 70 or more than 100 or more than 150 or more than 200 or in a range of 20 to 200 m or from 10 to 150 or from 20 to 100 , more preferably in a range of 30 to 80 m.
• the spray tower has a cylindrical geometry
• a height of the spray tower of more than 10 m for example of more than 15 m or of more than 20 m or of more than 25 m or of more than 30 m or in a range of 10 to 25 m, particularly preferably in a range of 15 to 20 m;
• the direction of the solder is understood to be the direction of the gravity vector.
• the flight path means the path that a droplet of slurry travels from the exit of the nozzle into the headspace of the spray tower to form granules until completion of the flight and fall operation.
• the flight and fall process will periodically end by impacting the granule at the bottom of the spray tower, or by granules coming into contact with other granules resting on the bottom of the spray tower, whichever comes first.
• the flight time is the time it takes for a granule to cover the flight path in the spray tower.
• the granules preferably have a helical trajectory in the spray tower.
• At least 60% by weight of the spray granules based on the total weight of the silica granules formed during the spray drying, have an average flight distance of more than 20 m, for example greater than 30 or greater than 50 or greater than 70 or more than 100 or more than 150 or more than 200 or in a range of 20 to 200 m or from 10 to 150 or from 20 to 100, particularly preferably in a range of 30 to 80 m.
• At least 70% by weight of the spray granules based on the total weight of the silica granules formed in the spray drying, have an average flight distance of more than 20 m, for example greater than 30 or greater than 50 or greater than 70 or more than 100 or more than 150 or more than 200 or in a range of 20 to 200 m or from 10 to 150 or from 20 to 100, particularly preferably in a range of 30 to 80 m.
• At least 80 wt .-% of the spray granules based on the total weight of the resulting during spray drying silica granules, a mean flight distance of more than 20 m back to Example of more than 30 or more than 50 or more than 70 or more than 100 or more than 150 or more than 200 or in a range of 20 to 200 m or from 10 to 150 or from 20 to 100, more preferably in a range of 30 to 80 m.
• At least 90% by weight of the spray granules based on the total weight of the silica granules formed in the spray drying, have an average flight distance of more than 20 m, for example greater than 30 or greater than 50 or greater than 70 or more than 100 or more than 150 or more than 200 or in a range of 20 to 200 m or from 10 to 150 or from 20 to 100, particularly preferably in a range of 30 to 80 m.
• a silica granule is obtained by roll granulating the slurry.
• Roll granulation is done by stirring the slurry in the presence of a gas at elevated temperature.
• Roll granulation preferably takes place in a stirred tank equipped with a stirring tool.
• the stirring container rotates in the opposite direction to the stirring tool.
• the stirring vessel further comprises an inlet through which silica powder can be introduced into the stirring vessel, an outlet through which silica granules can be removed, a gas inlet and a gas outlet.
• a pinworm is understood to mean a stirrer tool which is provided with a plurality of elongate pins whose longitudinal axis runs in each case coaxially with the axis of rotation of the stirrer tool.
• the movement sequence of the pins preferably describes coaxial circles about the axis of rotation.
• the slurry is adjusted to a pH of less than 7, for example to a pH in the range of 2 to 6.5, more preferably to a pH in the range of 4 to 6.
• a pH - Value is preferably an inorganic acid used, for example, an acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, particularly preferably hydrochloric acid.
• an atmosphere selected from air, an inert gas, at least two inert gases or a combination of air with at least one inert gas, preferably at least two inert gases.
• inert gases are preferably selected from the list consisting of nitrogen, helium, neon, argon, krypton and xenon.
• air, nitrogen or argon is present in the stirred tank, more preferably air.
• the atmosphere present in the stirred tank is part of a gas stream.
• the gas stream is preferably introduced into the stirred tank via the gas inlet and discharged via the gas outlet.
• the gas flow can take up further components in the stirred tank. These may originate from the slurry during roll granulation and pass into the gas stream.
• the stirred tank is preferably supplied with a dry gas stream.
• a "dry gas stream” is understood as meaning a gas or a gas mixture whose relative humidity is below the condensation point at the temperature set in the stirring vessel.
• the gas is preferably at a temperature in a range from 50 to 300 ° C., for example from 80 to 250 ° C, more preferably preheated from 100 to 200 ° C.
• 10 to 150 m 3 of gas per hour are preferably introduced per 1 kg of the slurry used into the stirred tank, for example 20 to 100 m 3 of gas per hour, more preferably 30 to 70 m 3 of gas per hour.
• the gas stream dries the slurry while stirring to form silica granules.
• the granules formed are removed from the stirred chamber.
• the withdrawn granules are further dried.
• the drying is carried out continuously, for example in a rotary kiln.
• Preferred temperatures for drying are in a range of 80 to 250 ° C, for example in a range of 100 to 200 ° C, more preferably in a range of 120 to 180 ° C.
• Continuously in the context of the present invention in relation to a method means that it can be operated continuously. This means that the supply and removal of substances and materials involved in the process can be carried out continuously during the execution of the process. It is not necessary to interrupt the procedure for this.
• Continuously as an attribute of an object, e.g. with respect to a "continuous furnace" means that this article is designed so that a process occurring in it or in it process step can be carried out continuously.
• the granules obtained by roll granulation can be screened.
• Sieving can be done before or after drying. Preference is given to sieving before drying. Granules having a particle size of less than 50 ⁇ m, for example having a particle size of less than 80 ⁇ m, are particularly preferably screened out with a particle size of less than 100 ⁇ m. Preference is given to granules having a particle size of more than 900 ⁇ m, for example having a particle size of more than 700 ⁇ m, and more preferably having a particle size of more than 500 ⁇ m.
• the sieving of larger particles can be carried out in principle by all methods known to the person skilled in the art and suitable for this purpose. The screening of larger particles preferably takes place by means of a vibrating trough.
• roll granulation is characterized by at least one, for example two or three, most preferably all of the following features:
• Granules with a particle size of less than 100 ⁇ and more than 500 ⁇ are sieved;
• the granules formed have a residual moisture of 15 to 30 wt .-%;
• the granules formed are dried at 80 to 250 ° C, preferably in a continuous drying tube, more preferably up to a residual moisture content of less than 1 wt .-%.
• the granulate obtained by granulation preferably by spray or roll granulation, also referred to as silica granules I, treated before it is processed into quartz glass bodies.
• This pretreatment can serve various purposes, which either facilitate the processing into quartz glass bodies or influence the properties of the resulting quartz glass bodies.
• the silica granules I may be compacted, cleaned, surface modified or dried.
• the silica granules I may be subjected to a thermal, mechanical or chemical treatment or a combination of two or more treatments to obtain a silica granule II.
• the silica granules I have a carbon content Wcpj.
• the carbon content Wcpj is preferably less than 50 ppm, for example less than 40 ppm or less than 30 ppm, more preferably in a range of from 1 ppb to 20 ppm, each based on the total weight of the silica granules I.
• the silica granule I comprises at least two particles.
• the at least two particles can perform a relative movement to each other.
• all measures known to the person skilled in the art and appearing suitable come into consideration as measures for generating the relative movement.
• Particularly preferred is a mixing.
• mixing can be carried out in any desired manner.
• a continuous furnace is selected for this purpose.
• the at least two particles can preferably perform a relative movement to each other by being moved in a continuous furnace, for example a rotary kiln.
• Continuous ovens are understood to mean furnaces in which the loading and unloading of the furnace, the so-called charging, takes place continuously.
• Examples of continuous furnaces are rotary kilns, roller kilns, conveyor ovens, drive-through ovens, push-through ovens.
• rotary kilns are used to treat the silica granules I.
• the silica granule I is treated with a reactant to obtain a silica granule II.
• the treatment is carried out to change the concentration of certain substances in the silica granules.
• the silica granules I may have impurities or certain functionalities whose content is to be reduced, such as: OH groups, carbon-containing compounds, transition metals, alkali metals and alkaline earth metals.
• the impurities and functionalities may originate from the starting material or be added during the process.
• the treatment of the silica granulate I can serve various purposes. For example, the use of treated silica granules I, ie, silica granules II, may facilitate the processing of the silica granules into quartz glass bodies. Furthermore, by this selection, the properties of the resulting quartz glass body can be adjusted. For example, the silica granules I can be purified or surface-modified. The treatment of the silica granulate I can therefore be used to improve the properties of the resulting quartz glass body.
• the reactants used are preferably a gas or a combination of several gases. This is also called gas mixture.
• the treatment is carried out in the presence of a gas or a combination of two or more as gases.
• the treatment is carried out in a gas countercurrent, or in a gas direct current.
• the reactant is selected from the group consisting of HCl, Cl 2 , F 2 , O 2 , O 3 or combinations of two or more thereof.
• mixtures of two or more of the aforementioned gases are used to treat silica granules I.
• metals contained as impurities in the silica granules I such as transition metals, alkali metals and alkaline earth metals can be removed.
• the aforementioned metals with constituents of the gas mixture can undergo gaseous compounds under the process conditions, which are subsequently discharged and thus no longer present in the granules.
• the OH content in the silica granules I can be reduced by treating the silica granules I with these gases.
• a gas mixture of HCl and Cl 2 is used as the reactant.
• the gas mixture has a content of HCl in a range from 1 to 30% by volume, for example in a range from 2 to 15% by volume, particularly preferably in a range from 3 to 10% by volume.
• the gas mixture has a content of Cl 2 in a range of 20 to 70 vol .-%, for example in a range of 25 to 65 vol .-%, particularly preferably in a range of 30 to 60 vol .-%.
• the remainder to 100% by volume may be supplemented by one or more inert gases, eg N 2 , He, Ne, Ar, Kr, or by air.
• the proportion of inert gas in reactants is in a range of 0 to less than 50% by volume, for example in a range of 1 to 40% by volume or from 5 to 30% by volume, more preferably in a range from 10 to 20% by volume, in each case based on the total volume of the reactant.
• O 2 , C 2 F 2 , or mixtures thereof with Cl 2 are preferably used to purify silica granule I prepared from a siloxane or a mixture of several siloxanes.
• the reactant in the form of a gas or gas mixture is preferably used as a gas stream or as part of a gas stream with a throughput in a range of 50 to 2000 L / h, for example in a range of 100 to 1000 L / h, more preferably in a range of 200 up to 500 L / h contacted with the silica granules.
• a preferred embodiment of the contacting is a contact of gas flow and silica granules in a continuous furnace, for example a rotary kiln.
• Another preferred embodiment of the contacting is a fluidized bed process.
• a silica granule II having a carbon content Wcp By treating the silica granule I with the reactant, a silica granule II having a carbon content Wcp) is obtained.
• the carbon content Wcp) of the silica granules II is smaller than the carbon content w C (i) of the silica granules I based on the total weight of the respective silica granules.
• Preference is w C ß) by 0.5 to 99%, for example by 20 to 80% or 50 to 95%, more preferably by 60 to 99% less than w C (i).
• the silica granule I is additionally subjected to a thermal or mechanical treatment or a combination of these treatments.
• One or more of these additional treatments may be before or during the treatment with the reactant.
• the additional treatment can also be carried out on the silica granules II.
• the general term "silica granules" used below includes the alternatives “silica granules I” and “silicon dioxide granules II.” It is also possible to apply the treatments described below to both the “silicon dioxide granules I" and the treated silicon dioxide granules I, the "silicon dioxide granules II".
• this treatment may facilitate the processing of the silica granules into quartz glass bodies
• the treatment may also affect the properties of the resulting quartz glass bodies
• the silica granules may be compacted, cleaned, surface modified or dried the specific surface area (BET) may decrease, and the bulk density and mean particle size may increase due to agglomeration of silica particles Namisch or static are performed.
• BET specific surface area
• all furnaces are suitable for the dynamic thermal treatment, in which the silicon dioxide granules can be thermally treated and thereby moved.
• the dynamic thermal treatment preferably continuous furnaces are used.
• a preferred average residence time of the silica granules in the dynamic thermal treatment is quantity dependent.
• the average residence time of the silica granules in the dynamic thermal treatment is preferably in the range from 10 to 180 minutes, for example in the range from 20 to 120 minutes or from 30 to 90 minutes.
• the average residence time of the silica granules in the dynamic thermal treatment in the range of 30 to 90 min.
• a defined portion of a stream of silica granules e.g. a gram, a kilogram or a ton. Beginning and end of the stay are determined here by running in and out of the continuous furnace operation.
• the throughput of the silica granules in a continuous process for dynamic thermal treatment is in the range of 1 to 50 kg / h, for example in the range of 5 to 40 kg / h or 8 to 30 kg / h. Particularly preferred is the throughput in the range of 10 to 20 kg / h.
• the treatment time results from the period between a loading and subsequent unloading of the furnace.
• the throughput is in a range of 1 to 50 kg / h, for example in the range of 5 to 40 kg / h or 8 to 30 kg / h.
• the throughput is particularly preferably in the range from 10 to 20 kg / h.
• the throughput can be achieved by a batch of a certain amount treated for one hour.
• the throughput may be achieved by a number of batches per hour, for example, the amount of a batch corresponding to the throughput per hour by the number of batches.
• the treatment time then corresponds to the fraction of an hour, which results from 60 minutes by the number of batches per hour.
• the dynamic thermal treatment of the silica granules preferably takes place at an oven temperature of at least 500 ° C., for example in the range from 510 to 1700 ° C. or from 550 to 1500 ° C. or from 580 to 1300 ° C., particularly preferably in the range from 600 to 1200 ° C.
• the oven in the oven chamber has the specified temperature.
• this temperature deviates upwards or downwards from the indicated temperature by less than 10%, based on the total treatment time and the entire length of the furnace, both at each time of treatment and at each point of the furnace.
• the continuous process of a dynamic thermal treatment of the silica granules can be carried out at different furnace temperatures.
• the oven may have a constant temperature over the treatment time, with the temperature varying in sections over the length of the oven. Such sections can be the same length or different lengths.
• a temperature which increases from the inlet of the furnace to the outlet of the furnace is preferred.
• the Temperature at the inlet at least 100 ° C lower than at the outlet, for example 150 ° C lower or 200 ° C lower or 300 ° C lower or 400 ° C lower. More preferably, the temperature at the exit is preferably at least 500 ° C., for example in the range from 510 to 1700 ° C.
• the temperature at the inlet is preferably at least 300 ° C, for example from 400 to 1000 ° C or from 450 to 900 ° C or from 500 to 800 ° C or from 550 to 750 ° C, more preferably from 600 to 700 ° C.
• each of the mentioned temperature ranges at the furnace inlet can be combined with each of the temperature ranges at the furnace outlet. Preferred combinations of furnace inlet and furnace outlet temperature ranges are:
• crucibles preferably are used in an oven.
• Crucibles or tin crucibles are suitable as crucibles.
• Rolled sheet crucibles of a plurality of plates riveted together are preferred.
• refractory metals are refractory metals, in particular tungsten, molybdenum and tantalum.
• the crucibles may also be formed from graphite or, in the case of crucibles of refractory metals, be lined with graphite foil. More preferably, the crucibles may be formed of silicon dioxide. Particular preference is given to using silicon dioxide crucibles.
• the average residence time of the silica granules in the static thermal treatment is quantity-dependent.
• the average residence time of the silica granules in the static thermal treatment at an amount of 20 kg of silica granules I in the range of 10 to 180 minutes, for example in the range of 20 to 120 minutes, more preferably in the range of 30 to 90 min.
• the static thermal treatment of the silica granules is carried out at an oven temperature of at least 800 ° C, for example in the range of 900 to 1700 ° C or 950 to 1600 ° C or 1000 to 1500 ° C or 1050 to 1400 ° C, especially preferably in the range of 1100 to 1300 ° C.
• the static thermal treatment of the silicon dioxide granules I preferably takes place at a constant oven temperature.
• the static thermal treatment can also be carried out at a varying oven temperature.
• the temperature increases in the course of the treatment, wherein the temperature at the beginning of the treatment by at least 50 ° C is lower than at the end, for example 70 ° C lower or 80 ° C lower or 100 ° C lower or 110 ° C lower, and wherein the temperature at the end is preferably at least 800 ° C, for example in the range of 900 to 1700 ° C or 950 to 1600 ° C or 1000 to 1500 ° C or 1050 to 1400 ° C, more preferably in Range from 1100 to 1300 ° C. mechanically
• the silicon dioxide granulate I can be treated mechanically.
• the mechanical treatment can be carried out to increase the bulk density.
• the mechanical treatment can be combined with the thermal treatment described above.
• By means of a mechanical treatment it can be avoided that the agglomerates in the silica granulate and thus the average particle size of the individual, treated silica granules in the silicon dioxide granules become too large. An enlargement of the agglomerates can complicate the further processing or have adverse effects on the properties of the quartz glass body produced by the method according to the invention, or a combination of the two effects.
• Mechanical treatment of the silica granules also promotes uniform contact of the surfaces of the individual silica granules with the gas or gases.
• the mechanical treatment of the silica granules may be accomplished by moving two or more silica granules in relative motion, for example, by rotating the tube of a rotary kiln.
• the silicon dioxide granulate I is preferably treated chemically, thermally and mechanically. In particular, a simultaneous chemical, thermal and mechanical treatment of the silica granules I.
• the silica granules I can be treated in a rotary kiln at elevated temperature under a chlorine- and oxygen-containing atmosphere. Water present in silica granules I evaporates, organic materials react to CO and CO 2 . Metal contaminants can be converted to volatile, chlorine-containing compounds.
• the chlorine-containing atmosphere contains, for example, HCl or CI 2 or a combination of both. This treatment causes a reduction of the carbon content.
• alkali and iron impurities are preferably reduced.
• a reduction in the number of OH groups is preferably achieved. At temperatures below 700 ° C, long treatment times may result, at temperatures above 1100 ° C there is a risk that close pores of the granules, including chlorine or gaseous chlorine compounds.
• the silicon dioxide granules I can only in a chlorine-containing atmosphere and then treated in an oxygen-containing atmosphere.
• the resulting low concentrations of carbon, hydroxyl groups and chlorine facilitate the melting of the silica granules II.
• step II.2) is characterized by at least one, for example by at least two or at least three, more preferably by a combination of all of the following features:
• the reactant includes HCl, CI 2 or a combination thereof;
• the treatment is carried out at a temperature in a range of 600 to 900 ° C; N4) the reactant forms a countercurrent;
• the reactant has a gas flow in a range of 50 to 2000 L / h, preferably 100 to 1000
• L / h more preferably 200 to 500 L / h;
• the reactant has a volume fraction of inert gas in a range of 0 to less than 50
• the silica granules I have a particle diameter which is larger than the particle diameter of the silica powder.
• the particle diameter of the silica granule I is up to 300 times larger than the particle diameter of the silica powder, for example up to 250 times greater or up to 200 times larger or up to 150 times larger or up to 100 times larger or up to 50 times larger or Up to 20 times larger or up to 10 times larger, more preferably 2 to 5 times larger.
• silica granules thus obtained are also referred to as silica granules II. More preferably, the silica granules II are obtained from the silica granules I in a rotary kiln by means of a combination of thermal, mechanical and chemical treatment.
• the silica granulate provided in step i.) Is preferably selected from the group consisting of silica granules I, silica granules II and a combination thereof.
• silicon dioxide granules I granules of silicon dioxide which are produced by granulation of silicon dioxide powder which was obtained in the pyrolysis of silicon compounds in a fuel gas flame.
• Silicon dioxide granules II is understood as meaning a granulate of silicon dioxide which is formed by post-treatment of the silicon dioxide granulate I. As after-treatment, chemical, thermal and / or mechanical treatments are contemplated in detail in the description of the provision of the silicon dioxide granules (process step II first object of the invention).
• the silicon dioxide granules provided in step i.) are particularly preferably the silicon dioxide granules I.
• the silicon granules I have the following features:
• a BET surface area in the range of 20 to 50 m 2 / g for example in a range of 20 to 40 m 2 / g; more preferably in a range of 25 to 35 m 2 / g;
• the microporous fraction preferably amounts to a BET surface area in the range from 4 to 5 m 2 / g; for example, in a range of 4.1 to 4.9 m 2 / g; more preferably in a range of 4.2 to 4.8 m 2 / g; and
• [B] an average particle size in a range of 180 to 300 ⁇ .
• the Sihziumdioxidgranulat I is preferably characterized by at least one, for example by at least two or at least three or at least four, more preferably by at least five of the following features:
• [C] has a bulk density in a range of 0.5 to 1.2 g / cm 3 , for example, in a range of 0.6 to 1.1 g / cm 3 , more preferably in a range of 0.7 to 1 , 0 g / cm 3 ;
• [E] has an aluminum content of less than 200 ppb, preferably less than 100 ppb, for example less than 50 ppb or from 1 to 200 ppb or from 15 to 100 ppb, more preferably in a range from 1 to 50 ppb.
• [G] a pore volume in a range of 0.1 to 1.5 mL / g, for example in a range of 0.15 to 1.1 mL / g; more preferably in a range of 0.2 to 0.8 mL / g,
• Metal content of metals other than aluminum of less than 1000 ppb preferably in a range of 1 to 900 ppb, for example in a range of 1 to 700 ppb, more preferably in a range of 1 to 500 ppb ;
• [J] has a residual moisture of less than 10% by weight, preferably in a range of from 0.01% by weight to
• wt .-% for example from 0.02 to 1 wt .-%, particularly preferably from 0.03 to 0.5 wt .-%; wherein the wt .-%, ppm and ppb are each based on the total weight of the silica granules I.
• the OH content also hydroxy group content, is understood as meaning the content of OH groups in a material, for example in silica powder, in granules of silicon dioxide or in a quartz glass body. Of the Content of OH groups is determined spectroscopically after in the infrared by comparison of the first and the third OH band.
• the chlorine content is understood as meaning the content of elemental chlorine or chloride ions in the silicon dioxide granules, the silicon dioxide powder or the quartz glass body.
• the aluminum content is understood as meaning the content of elemental aluminum or aluminum ions in the silicon dioxide granules, the silicon dioxide powder or the quartz glass body.
• the silica granule I has a microporous fraction in a range of 4 to 5 m 2 / g; for example, in a range of 4.1 to 4.9 m 2 / g; more preferably in a range of 4.2 to 4.8 m 2 / g.
• the silica granulate I preferably has a density in a range of 2.1 to 2.3 g / cm 3 , more preferably in a range of 2.18 to 2.22 g / cm 3 .
• the silicon dioxide granulate I preferably has an average particle size in a range from 180 to 300 ⁇ m, for example in a range from 220 to 280 ⁇ m, particularly preferably in a range from 230 to 270 ⁇ m.
• the Siliziumdioxidgranulat I preferably has a particle size D 50 in the range of 150 to 300 ⁇ , for example in a range from 180 to 280 ⁇ , more preferably ⁇ in a range of 220 to 270th
• the silica granules I a particle size D 10 in a range of 50 to 150 ⁇ , for example in a range of 80 to 150 ⁇ , more preferably in a range of 100 to 150 ⁇ on.
• the granular silica I has a particle size D 90 in a range of 250 to 620 ⁇ , for example in a range of 280 to 550 ⁇ , more preferably in a range of 300 to 450 ⁇ on.
• the silica granulate I preferably has the combination of features [A] / [B] / [C] or [A] / [B] / [E] or [A] / [B] / [G], more preferably the combination of features [A ] / [B] / [C] / [E] or [A] / [B] / [C] / [G] or [A] / [B] / [E] / [G], particularly preferably the combination of features [A] / [B] / [C] / [e] / [G].
• the silica granulate I preferably has the combination of features [A] / [B] / [C], wherein the BET surface area in a range of 20 to 40 m 2 / g, the average particle size in a range of 180 to 300 ⁇ and the Bulk density is in a range of 0.6 to 1.1 g / mL.
• the silica granulate I preferably has the combination of features [A] / [B] / [E], wherein the BET surface area in a range of 20 to 40 m 2 / g, the average particle size in a range of 180 to 300 ⁇ and the Aluminum content is in a range of 1 to 50 ppb.
• the silica granulate I preferably has the combination of features [A] / [B] / [G], wherein the BET surface area in a range of 20 to 40 m 2 / g, the average particle size in a range of 180 to 300 ⁇ and the Pore volume is in a range of 0.2 to 0.8 mL / g.
• the silica granulate I preferably has the combination of features [A] / [B] / [C] / [E], wherein the BET surface area in a range of 20 to 40 m 2 / g, the average particle size in a range of 180 to 300 ⁇ , the bulk density in a range of 0.6 to 1.1 g / mL and the aluminum content in a range of 1 to 50 ppb.
• the silica granulate I preferably has the combination of features [A] / [B] / [C] / [G], wherein the BET surface area in a range of 20 to 40 m 2 / g, the average particle size in a range of 180 to 300 ⁇ , the bulk density in a range of 0.6 to 1.1 g / mL and the pore volume in a range of 0.2 to 0.8 mL / g.
• the silica granulate I preferably has the combination of features [A] / [B] / [E] / [G], wherein the BET surface area in a range of 20 to 40 m 2 / g, the average particle size in a range of 180 to 300 ⁇ , the aluminum content in a range of 1 to 50 ppb and the pore volume in a range of 0.2 to 0.8 mL / g.
• the silica granulate I preferably has the combination of features [A] / [B] / [C] / [E] / [G], wherein the BET surface area in a range of 20 to 40 m 2 / g, the average particle size in a Range from 180 to 300 ⁇ , the bulk density in a range of 0.6 to 1.1 g / mL, the aluminum content in a range of 1 to 50 ppb and the pore volume in a range of 0.2 to 0.8 mL / g is.
• Particle size is understood to mean the size of the particles composed of the primary particles which are present in a silica powder, in a slurry or in a silica granulate.
• the mean particle size is understood as meaning the arithmetic mean of all particle sizes of said substance.
• the D 50 value indicates that 50% of the particles, based on the total number of particles, are smaller than the specified value.
• the D 10 value indicates that 10% of the particles, based on the total number of particles, are smaller than the specified value.
• the D 90 value indicates that 90% of the particles, based on the total number of particles, are smaller than the specified value.
• the particle size is determined by dynamic image analysis method according to ISO 13322-2: 2006-11.
• the silicon dioxide granules provided in step i.) are the silicon dioxide granules II.
• the silicon dioxide granules II have the following features:
• the silicon dioxide granules II preferably have at least one, for example at least two or at least three or at least four, more preferably at least five of the following characteristics:
• (C) a bulk density in a range of 0.7 to 1.2 g / cm 3 , for example, in a range of 0.75 to 1.1 g / cm 3 , particularly preferably in a range of 0.8 to 1 , 0 g / cm 3 ;
• (G) a pore volume in a range of 0.1 to 2.5 mL / g, for example, in a range of 0.2 to 1.5 mL / g; more preferably in a range of 0.4 to 1 mL / g;
• (H) a chlorine content of less than 500 ppm, preferably less than 400 ppm, for example less than 350 ppm or preferably less than 330 ppm or in a range from 1 ppb to 500 ppm or from 10 ppb to 450 ppm particularly preferred from 50 ppb to 300 ppm;
• wt .-%, ppm and ppb are each based on the total weight of the silica granules II.
• the Sihziumdioxidgranulat II has a microporous fraction in a range of 1 to 2 m 2 / g, for example in a range of 1.2 to 1.9 m 2 / g, more preferably in a range of 1.3 to 1.8 m 2 / g on.
• the silicon dioxide granule II preferably has a density in a range from 0.5 to 2.0 g / cm 3 , for example from 0.6 to 1.5 g / cm 3 , particularly preferably from 0.8 to 1.2 g / cm 3 up.
• the density is determined according to the method described in the test methods.
• the Sihziumdioxidgranulat II preferably has a particle size D 50 in a range of 150 to 250 ⁇ , for example in a range of 180 to 250 ⁇ , more preferably in a range of 200 to 250 ⁇ . Further preferably, the Sihziumdioxidgranulat II has a particle size D 10 in a range of 50 to 150 ⁇ , for example in a range of 80 to 150 ⁇ , more preferably in a range of 100 to 150 ⁇ on. Further preferably, the Sihziumdioxidgranulat II has a particle size D 90 in a range of 250 to 450 ⁇ , for example in a range of 280 to 420 ⁇ , more preferably in a range of 300 to 400 ⁇ on.
• the silica granule II preferably has the feature combination (A) / (B) / (D) or (A) / (B) / (F) or (A) / (B) / (I), more preferably the combination of features (A ) / (B) / (D) / (F) or (A) / (B) / (D) / (I) or (A) / (B) / (F) / (I), particularly preferably the combination of features (A) / (B) / (D) / (F) / (I).
• the silica granule II preferably has the feature combination (A) / (B) / (D), wherein the BET surface area is in a range of 10 to 30 m 2 / g, the mean particle size is in a range of 150 to 280 ⁇ and the carbon content is less than 4 ppm.
• the silica granules II preferably has the combination of features (A) / (B) / (F), wherein the BET surface area in a range of 10 to 30 m 2 / g, the average particle size in a range of 150 to 280 ⁇ and the Tamping density is in a range of 0.8 to 1.0 g / mL.
• the silica granules II preferably has the combination of features (A) / (B) / (I), wherein the BET surface area in a range of 10 to 30 m 2 / g, the average particle size in a range of 150 to 280 ⁇ and the Metal content of metals other than aluminum in a range of 1 to 400 ppb.
• the silica granule II preferably has the feature combination (A) / (B) / (D) / (F), wherein the BET surface area is in a range of 10 to 30 m 2 / g, the average particle size in a range of 150 to 280 ⁇ , the carbon content is less than 4 ppm and the tamped density is in a range of 0.8 to 1.0 g / mL.
• the silica granule II preferably has the feature combination (A) / (B) / (D) / (I), wherein the BET surface area is in a range of 10 to 30 m 2 / g, the average particle size in a range of 150 to 280 ⁇ , the carbon content is less than 4 ppm, and the metal content of metals other than aluminum is in a range of 1 to 400 ppb.
• the silica granule II preferably has the feature combination (A) / (B) / (F) / (I), wherein the BET surface area in a range of 10 to 30 m 2 / g, the average particle size in a range of 150 to 280 ⁇ , the tamped density in a range of 0.8 to 1.0 g / mL and the metal content of metals other than aluminum, in a range of 1 to 400 ppb.
• the silica granule II preferably has the feature combination (A) / (B) / (D) / (F) / (I), wherein the BET surface area is in a range of 10 to 30 m 2 / g, the average particle size in is a range of 150 to 280 ⁇ m, the carbon content is less than 4 ppm, the tamped density is in a range of 0.8 to 1.0 g / ml, and the metal content of metals other than aluminum is in a range of 1 to 400 ppb.
• Step ii) From the silicon dioxide granules provided in step i) a glass melt is formed.
• the silica granules are heated to obtain the glass melt.
• the heating of the silicon dioxide granules to obtain a molten glass can in principle be carried out in any way known to the person skilled in the art for this purpose.
• the heating of the silica granules to obtain a molten glass may be carried out by vacuum sintering.
• This process is a batch process in which the silica granules are batch-heated to melt.
• the silica granules are heated in an evacuable crucible.
• the crucible is arranged in a melting furnace.
• the crucible can be arranged standing or hanging, preferably hanging.
• the crucible may be a sintered crucible or tin crucible.
• Rolled sheet crucibles of a plurality of plates riveted together are preferred.
• Refractory metals, in particular W, Mo and Ta, graphite or graphite foil lined crucibles are suitable, for example, as crucible material; graphite crucibles are particularly preferred.
• Vacuum is understood as meaning a residual pressure of less than 2 mbar.
• the crucible containing the silicon dioxide granules is evacuated to a residual pressure of less than 2 mbar.
• the crucible is heated in the furnace to a melting temperature in the range of 1500 to 2500 ° C, for example in the range of 1700 to 2300 ° C, more preferably in the range of 1900 to 2100 ° C.
• the preferred holding time of the silica granules in the crucible at the melting temperature is quantity dependent.
• the holding time of the silica granules in the crucible at the melting temperature is preferably 0.5 to 10 hours, for example 1 to 8 hours or 1.5 to 6 hours, more preferably 2 to 5 hours.
• the silica granules can be agitated when heated.
• the movement of the silicon dioxide granules is preferably carried out by stirring, shaking or panning.
• the heating of the silica granules to obtain a molten glass can be done by gas pressure sintering. This process is a static process in which the silica granules are heated batchwise in batches.
• the silica granules are placed in a sealable crucible and placed in a melting furnace.
• a sealable crucible For example, graphite, refractory metals, in particular W, Mo and Ta, or graphite foil-lined crucibles are suitable as crucible material; graphite crucibles are particularly preferred.
• the crucible comprises at least one gas inlet and at least one gas outlet. Through the gas inlet can gas in the Crucible interior be initiated. Through the gas outlet gas can be discharged from the crucible interior. It is preferably possible to operate the crucible in the gas stream and in a vacuum.
• the silica granules are heated to melt in the presence of at least one gas or two or more gases.
• gases are, for example, H 2 , and inert gases (N 2 , He, Ne, Ar, Kr) and two or more thereof.
• the gas pressure sintering is preferably carried out in a reducing atmosphere, particularly preferably in the presence of H 2 or H 2 / He. There is a gas exchange of air for H 2 or H 2 / He instead.
• the silicon dioxide granules are preferably heated to melt at a gas pressure of more than 1 bar, for example in the range from 2 to 200 bar or from 5 to 200 bar or from 7 to 50 bar, particularly preferably from 10 to 25 bar.
• the crucible is heated in the oven to a melting temperature in the range of 1500 to 2500 ° C, for example in the range of 1550 to 2100 ° C or 1600 to 1900 ° C, more preferably in the range of 1650 to 1800 ° C.
• the preferred holding time of the silica granules in the crucible at the melting temperature under gas pressure is quantity-dependent.
• the holding time of the silica granules in the crucible at the melting temperature in an amount of 20 kg 0.5 to 10 hours, for example 1 to 9 hours or 1.5 to 8 hours, more preferably 2 to 7 hours.
• the silicon dioxide granules are preferably first melted in vacuo, then in an H 2 atmosphere or an atmosphere comprising H 2 and He, more preferably in a countercurrent of these gases.
• the temperature in the first step is preferably lower than in the next step.
• the temperature difference between the heating in vacuum and in the presence of the gas or gases is preferably 0 to 200 ° C, for example 10 to 100 ° C, particularly preferably 20 to 80 ° C.
• the silica granules are pretreated before melting.
• the silica granules may be heated so that an at least partially crystalline phase is formed before the semi-crystalline silica granules are heated to melt
• the silica granules are preferably heated at reduced pressure or in the presence of one or more gases.
• gases are, for example, HCl, Cl 2 , F 2 , O 2 , H 2 , C 2 F 6 , air, inert gas (N 2 , He, Ne, Ar, Kr) and two or more thereof.
• the silica granules are heated at reduced pressure.
• the silica granules are heated to a treatment temperature at which the silica granules soften without completely melting, for example at a temperature in the range from 1000 to 1700 ° C or from 1100 to 1600 ° C or from 1200 to 1500 ° C, more preferably to a temperature in the range of 1250 to 1450 ° C.
• the silica granules are heated in a crucible located in an oven.
• the crucible can be arranged standing or hanging, preferably hanging.
• the crucible may be a sintered crucible or a tin crucible.
• Rolled sheet crucibles of a plurality of plates riveted together are preferred.
• Refractory metals, in particular W, Mo and Ta, graphite or graphite foil lined crucibles are suitable, for example, as crucible material; preference is given to graphite crucibles.
• the holding time of the silica granules in the crucible at the treatment temperature is 1 to 6 hours, for example 2 to 5 hours, more preferably 3 to 4 hours.
• the silica granules are heated in a continuous process, more preferably in a rotary kiln.
• the average residence time in the oven is preferably 10 to 180 minutes, for example 20 to 120 minutes, more preferably 30 to 90 minutes.
• the furnace used for the pretreatment may be integrated in the feed to the furnace where the silica granules are heated to melt. More preferably, the pretreatment may be carried out in the smelting furnace.
• the method is characterized in that during the heating during a period of time t T a temperature T T is kept which is below the melting temperature of silicon dioxide.
• the temperature T T is in a range of 1000 to 1700 ° C.
• the heating is carried out by heating in two stages, particularly preferably first heated to a temperature T TJ of 1000 to 1400 ° C and then to a temperature T T2 of 1600 to 1700 ° C.
• the period t T is in a range of 1 to 20 hours, preferably from 2 to 6 hours.
• the period t T1 having the temperature T T1 is in a range of 1 to 10 hours and the period t T2 having the temperature T T2 is in a range of 1 to 10 hours.
• the temperature T T is for a period t T in a particular area. So preferred combinations of temperature T T and period t T are given in the following table:
• the period of time T T is prior to forming the glass melt.
• a quartz glass body is formed.
• the quartz glass body is formed from at least part of the glass melt formed in step ii).
• the quartz glass body can be formed from at least part of the glass melt in the crucible or after removal of at least a portion of the glass melt from the crucible, preferably after removal of at least a portion of the glass melt from the crucible.
• the removal of a portion of the glass melt produced in step ii) can be carried out continuously from the melting furnace or the melting chamber, or after completion of the preparation of the glass melt. Preferably, a part of the molten glass is removed continuously. The molten glass is removed through the outlet from the furnace or the outlet of the melting chamber, preferably via a nozzle.
• the molten glass may be cooled before, during or after removal to a temperature which allows the molten glass to be molded. With the cooling of the molten glass, an increase in the viscosity of the molten glass is connected.
• the molten glass is preferably cooled to the extent that the formed form is retained during molding and molding can be carried out simultaneously as quickly as possible, reliably and with little effort. The person skilled in the art can easily determine the viscosity of the molten glass for molding by varying the temperature of the molten glass on the mold.
• the molten glass is cooled to a temperature of less than 500 ° C, for example less than 200 ° C or less than 100 ° C or less than 50 ° C, more preferably a temperature in the range of 20 to 30 ° C.
• the cooling takes place at a rate in a range of 0.1 to 50 K / min, for example from 0.2 to 10 K / min or from 0.3 to 8 K / min or from 0.5 to 5 K. / min, more preferably in a range of 1 to 3 K / min.
• the formed quartz glass body may be a solid body or a hollow body.
• a solid body is meant a body consisting essentially of a single material.
• a solid body may have one or more inclusions, eg, gas bubbles.
• Such inclusions in a solid body often have a size of 65 mm 3 or less, for example less than 40 mm 3 , or less than 20 mm 3 , or less than 5 mm 3 'or less than 2 mm 3 , more preferably less than 0.5 mm 3 .
• the quartz glass body has an outer shape.
• the outer shape is understood to be the shape of the outer edge of the cross section of the quartz glass body.
• the outer shape of the quartz glass body is preferably round, elliptical or polygonal in cross-section with three or more corners, for example 4, 5, 6, 7 or 8 corners, more preferably the quartz glass body is round.
• the quartz glass body has a length in the range of 100 to 10,000 mm, for example from 1000 to 4000 mm, more preferably from 1200 to 2000 mm.
• the quartz glass body has an outer diameter in the range of 10 to 1500 mm, for example in a range of 50 to 1000 mm or 100 to 500 mm, more preferably in a range of 150 to 300 mm.
• the molding of the quartz glass body takes place by means of a nozzle.
• the molten glass is passed through the nozzle.
• the outer shape of a quartz glass body formed by the nozzle is determined by the shape of the opening of the nozzle.
• a cylinder is formed as the quartz glass body is formed.
• the nozzle may be integrated into the smelting furnace or arranged separately. If the nozzle is not integrated in the smelting furnace, it may be equipped with an upstream container in which the molten glass is introduced after melting and before molding.
• the molding of the quartz glass body can be done by forming the glass melt in a mold, for example in a molded crucible.
• the molten glass is cooled in the mold and then removed therefrom.
• the quartz glass body is cooled after forming.
• the quartz glass body is cooled to a temperature of less than 500 ° C, for example of less than 200 ° C or less than 100 ° C or less than 50 ° C, more preferably to a temperature in the range of 20 to 30 ° C.
• the quartz glass body formed in step iii.) Is preferably at a rate in the range from 0.1 to 50 K / min, for example from 0.2 to 10 K / min or from 0.3 to 8 K / min or from 0 , 5 to 5 K / min, more preferably in a range of 1 to 3 K / min cooled to room temperature (25 ° C). This cooling preferably takes place in the melt form.
• the quartz glass body is cooled at least up to a temperature of 1300 ° C at a rate of up to 5 K / min.
• the cooling of the quartz glass body in a temperature range of 1300 to 1000 ° C at a rate of not more than 1 K / min.
• the quartz glass body is cooled from a temperature of below 1000 ° C at a rate of up to 50 K / min.
• the cooling takes place according to the following profile:
• the process according to the invention preferably comprises the following process step:
• the formed hollow body has an inner and an outer shape.
• Inner form is understood to mean the shape of the inner edge of the hollow body in cross section.
• the inner and outer shape of the cross section of the hollow body may be the same or different.
• the inner and outer shapes of the hollow body may be round, elliptical or polygonal in cross-section with three or more corners, for example 4, 5, 6, 7 or 8 corners.
• the outer shape of the cross section corresponds to the inner shape of the cross section of the hollow body.
• the hollow body in cross section has a round inner and a round outer shape.
• the hollow body may differ in the inner and outer shape.
• the hollow body in cross section has a round outer shape and a polygonal inner shape.
• the hollow body has a round outer shape and a hexagonal inner shape in cross section.
• the hollow body has a length in the range of 100 to 10,000 mm, for example from 1000 to 4000 mm, more preferably from 1200 to 2000 mm.
• the hollow body has a wall thickness in a range of 1 to 1000 mm, for example in a range of 10 to 500 mm or from 30 to 200 mm, particularly preferably in a range of 50 to 125 mm.
• the hollow body has an outer diameter of 10 to 1500 mm, for example in a range of 50 to 1000 mm or 100 to 500 mm, more preferably in a range of 150 to 300 mm.
• the hollow body preferably has an inner diameter of 1 to 500 mm, for example in a range of 5 to 300 mm or of 10 to 200 mm, particularly preferably in a range of 20 to 100 mm.
• the hollow body contains one or more openings.
• the hollow body preferably contains an opening.
• the hollow body preferably contains an even number of openings, for example 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20 openings.
• the hollow body contains two openings.
• the hollow body is a tube. This shape of the hollow body is particularly preferred when the optical fiber includes only one core.
• the hollow body may contain more than two openings.
• the openings are preferably in pairs opposite each other in the ends of the quartz glass body.
• each end of the quartz glass body has 2, 3, 4, 5, 6, 7 or more than 7 openings, more preferably 5, 6 or 7 openings.
• the hollow body can in principle be formed in any way known to those skilled in the art.
• the hollow body is formed by means of a nozzle.
• the nozzle in the center of its opening contains a device which dissipates the molten glass during molding.
• a hollow body can be formed from a molten glass.
• a hollow body can be done by using a nozzle and subsequent aftertreatment.
• all processes known to the person skilled in the art for producing a hollow body from a solid body for example the swaging of channels, drilling, honing or grinding, are suitable as aftertreatment.
• As a post-treatment it is preferable to guide the solid body over one or more spikes, whereby a hollow body is formed.
• the mandrel can be introduced into the solid body to form a hollow body.
• the hollow body is cooled after forming.
• the molding into a hollow body can be done by forming the glass melt in a mold, for example in a molded crucible.
• the molten glass is cooled in the mold and then removed therefrom.
• the cooling can preferably be done by cooling the mold from the outside.
• the hollow body is cooled to a temperature of less than 500 ° C, for example of less than 200 ° C or less than 100 ° C or less than 50 ° C, more preferably to a temperature in the range of 20 to 30 ° C.
• the hollow body formed in step iii.) Is preferably at a speed in the range from 0.1 to 50 K / min, for example from 0.2 to 10 K / min or from 0.3 to 8 K / min or from 0 , 5 to 5 K / min, more preferably in a range of 1 to 3 K / min cooled to room temperature (25 ° C).
• the hollow body is cooled at least up to a temperature of 1300 ° C at a rate of up to 5 K / min.
• the cooling of the quartz glass body in a temperature range of 1300 to 1000 ° C at a rate of not more than 1 K / min.
• the hollow body is cooled from a temperature of below 1000 ° C at a rate of up to 50 K / min.
• the cooling of the hollow body preferably takes place according to the following profile:
• the quartz glass body formed by the method according to the first aspect of the invention has the following properties:
• C] has an aluminum content of less than 200 ppb, for example less than 100 ppb, more preferably less than 80 ppb;
• ppb and ppm are each based on the total weight of the quartz glass body.
• the quartz glass body formed according to the first article is transparent and poor in bubbles.
• transparent is understood to mean the transmittance of light in the visible range, and the intensity of the incident light to the intensity of the emergent light in the range from 400 to 700 nm is preferably at least 80%.
• a quartz glass body has at least one, for example at least two or at least three or at least four, more preferably at least five of the following features:
• a metal content of metals other than aluminum of less than 300 ppb, for example of less than 200 ppb, more preferably in a range of from 1 to 150 ppb;
• K] has a refractive index homogeneity of less than lxl 0 "4 , for example less than 5xl0 " 5 , more preferably less than lxl 0 "6 ;
• the quartz glass body preferably has the combination of features A] / B] / C] / D] or A] / B] / C] / E] or A] / B] / C] / G], more preferably the combination of features A] / B] / C] / D] / E] or A] / B] / C] / D] / G] or A] / B] / C] / E] / G], particularly preferably the combination of features A] / B ] / C] / D] / e] / G.
• the quartz glass body preferably has the combination of features A] / B] / C] / D], wherein the OH content is less than 5 ppm, the chlorine content less than 60 ppm, the aluminum content less than 100 ppb and the fictitious temperature in a range of 1055 and 1200 ° C.
• the quartz glass body preferably has the combination of features A] / B] / C] / E], the OH content being less than 5 ppm, the chlorine content being less than 60 ppm, the aluminum content being less than 100 ppb and the ODC content being in one Range of ⁇ , ⁇ 15 to 3xl0 15 / cm 3 .
• the quartz glass body preferably has the combination of features A] / B] / C] / D] / E], wherein the OH content is less than 5 ppm, the chlorine content is less than 60 ppm, the aluminum content is less than 100 ppb, the fictitious temperature in a range of 1055 and 1200 ° C and the ODC content in a range of ⁇ , ⁇ 15 to 3xl0 15 / cm 3 .
• a second object of the present invention is a quartz glass body obtainable by the method according to the first aspect of the invention.
• a third aspect of the present invention is a quartz glass body containing fumed silica, the fused silica body having the following features:
• C] has an aluminum content of less than 200 ppb
• ppb and ppm are each based on the total weight of the quartz glass body.
• the quartz glass body is preferably characterized by at least one, for example at least two or at least three or at least four, particularly preferably all of the following features:
• an ODC content of less than 5xl0 15 / cm 3 for example in a range of ⁇ , ⁇ 15 to 3xl0 15 / cm 3 , more preferably in a range of 0.5xl0 15 to 2.0xl0 15 / cm 3 ;
• a metal content of metals other than aluminum of less than 300 ppb, for example of less than 200 ppb, more preferably in a range of from 1 to 150 ppb;
• K a refractive index homogeneity of less than lxlO "4, for example of less than 5xl0" 5, particularly preferably of less than lxl 0 "6;
• ppb and ppm are each based on the total weight of the quartz glass body.
• the quartz glass body preferably has a homogeneously distributed OH quantity, amount of chlorine or amount of aluminum.
• An indicator of the homogeneity of the silica glass body can be expressed in the standard deviation of the OH amount, the amount of chlorine or the amount of aluminum.
• the standard deviation is the measure of the spread of the values of a variable, here the OH quantity, amount of chlorine or amount of aluminum, by their arithmetic mean.
• the content of the component to be determined in the sample for example OH, chlorine or aluminum, is determined at at least seven measurement points.
• a fourth subject of the invention is a method for producing a shaped body comprising the following method steps:
• the quartz glass body provided in step (1) is a quartz glass body according to the second or third aspect of the invention or obtainable by a method according to the first aspect of the invention.
• the provided quartz glass body has the features described in the first, second or third aspect of the invention.
• the formation of the shaped body from the quartz glass body can in principle be carried out in any manner known to the person skilled in the art and appear to be suitable for the present purpose.
• the forming is molding.
• the quartz glass body as described in the context of the first subject of the invention is formed into a shaped body. More preferably, the shaped body can be formed by means of techniques known to glass blowers.
• the shaped body can assume any shape which can be shaped from quartz glass.
• Preferred shaped bodies are, for example:
• Hollow body with at least one opening such as round-bottomed flasks and stand-up flasks,
• Tubes and hollow cylinders for example reaction tubes, profile tubes, rectangular chambers, rods, rods and blocks, for example in a round or angular, symmetrical or asymmetrical design,
• bent parts for example convex or concave surfaces and plates, bent bars and tubes.
• the shaped body can be treated after molding.
• all methods described in connection with the first subject of the invention which are suitable for reworking the quartz glass body come into consideration.
• the shaped body can be mechanically processed, for example by drilling, honing, external grinding, crushing or drawing.
• a fifth aspect of the invention relates to a molded article obtainable by a process according to the fourth aspect of the invention.
• the procedure includes the following steps:
• the steps (1) and (2) are preferably characterized by the features described in the context of the fourth subject.
• the shaped body is preferably characterized by the features described in the context of the fourth article.
• a sixth subject of the present invention relates to a method for producing a structure comprising the following method steps:
• the aforementioned part may include quartz glass or a material other than quartz glass, or may be made of this material.
• the material is preferably selected from the group consisting of glass, metal, ceramic and plastic, or a combination of the aforementioned materials.
• the bonding of the shaped body to the part or parts can in principle be carried out in any known manner known to those skilled in the art for joining the shaped body to the part or parts.
• Preferred types of bonding are in each case independently of one another for each individual compound, in particular compounds produced by material bond or positive connection.
• Preferred compounds by material connection are welding and gluing.
• Preferred connections by positive engagement are screws, presses and rivets. Further preferred combinations of positive engagement and material connection in a single compound, for example screws and at the same time gluing, or in the case of several compounds present within a structure can be selected.
• the structure has homogeneous material properties. These include preferably a homogeneous material distribution, a homogeneous viscosity distribution, homogeneous optical properties and combinations thereof.
• a seventh aspect of the present invention relates to a structure obtainable by the above-described method of manufacturing a structure according to the invention (sixth aspect of the invention). For this purpose, reference is made to the aspects and embodiments described above.
• FIG. 4 schematic representation of a spray tower
• FIG. 6 shows a flowchart (method for producing a shaped body)
• FIG. 1 shows a flow chart containing steps 101 to 104 of a method 100 for producing a quartz glass body according to the present invention.
• a silica granulate is provided in a first step 101.
• a glass melt is formed from the silica granules in a second step 102.
• molds are used for melting, which can be introduced into an oven and removed from it again.
• Such forms are often made of graphite. They result in a negative mold of the casting.
• the silica granules are filled into the mold, first melted in the mold in the third step 103.
• the quartz glass body is formed in the same mold by cooling the melt.
• This is then removed from the mold and processed further, for example in an optional step 104.
• This procedure is discontinuous.
• the formation of the melt takes place preferably at reduced pressure, especially at vacuum. It is also possible to temporarily charge the furnace with a reducing, hydrogen-containing atmosphere during step 103.
• a quartz glass body is formed.
• the formation of the quartz glass body takes place here by removing at least a portion of the glass melt from the crucible and cooling, for example by a nozzle at the lower end of the crucible.
• the shape of the quartz glass body can be determined by the design of the nozzle.
• massive bodies can be obtained. Hollow bodies are obtained, for example, if a mandrel is additionally provided in the nozzle.
• This exemplary method for the production of quartz glass bodies, and in particular step 103 is preferably carried out continuously.
• a hollow body can be formed from a solid quartz glass body.
• FIG. 2 shows a flow chart containing the steps 201, 202 and 203 of a method 200 for producing a silicon dioxide granulate I.
• a silicon dioxide powder is provided.
• a silica powder is preferably obtained from a synthetic process in which a silicon-containing material, for example, a siloxane, a silicon alkoxide or a silicon halide is converted to silica in a pyrogenic process.
• the silica powder is mixed with a liquid, preferably water, to obtain a slurry.
• the silica contained in the slurry is transferred to a silica granule.
• the granulation takes place by means of spray granulation. For this, the slurry is sprayed through a nozzle into a spray tower and dried to form granules, with the contact surface between the nozzle and the slurry including a glass or plastic.
• FIG. 3 shows a flow chart containing the steps 301, 302, 303 and 304 of a method 300 for producing a silica granulate II.
• the steps 301, 302 and 303 run in accordance with the steps 201, 202 and 203 according to FIG in step 303, silica granules I obtained are processed into a silica granulate II. This is preferably done by heating the silica granules I in a chlorine-containing atmosphere.
• FIG. 4 shows a preferred embodiment of a spray tower 1100 for spray granulation of silicon dioxide.
• the spray tower 1100 includes a feeder 1101 through which a pressurized slurry containing silica powder and a liquid is supplied to the spray tower.
• a nozzle 1 102 At the end of the line is a nozzle 1 102, through which the slurry is finely distributed in the spray tower is introduced.
• the nozzle is oriented obliquely upwardly so that the slurry is sprayed as fine droplets in the direction of the nozzle alignment in the spray tower and then falls down in a bow driven by gravity.
• a gas inlet 1 103 At the upper end of the spray tower is a gas inlet 1 103.
• the spray tower 1 100 also comprises a sighting device 1 104 and a screening device 1105.
• the sighting device 1 104 particles are sucked off, which fall below a defined particle size, and removed by the discharge 1 106. According to the particle size of the particles to be sucked, the suction strength of the sighting device 104 can be regulated.
• sieve 1 105 particles are screened above a defined particle size and removed by the discharge 1 107. Depending on the particle size of the particles to be sieved, the sieve permeability of the sieving apparatus 1105 can be selected.
• FIG. 5 shows a preferred embodiment of a furnace 1500 suitable for a vacuum sintering process, a gas pressure sintering process, and especially a combination thereof.
• the oven has a pressure-resistant casing 1501 and a thermal insulating layer 1502 from outside to inside.
• the enclosed space referred to as the furnace interior, can be acted upon by a gas feed 1504 with a gas or a gas mixture.
• the oven interior is provided with a gas outlet 1505, can be removed via the gas.
• melt molds 1508 can be introduced with melt 1509.
• the melt mold 1508 may be on one side be open (shown here) or the melt 1509 completely surrounded (not shown).
• FIG. 6 shows a flow chart containing the steps 1601 and 1602 of a method for producing a shaped body.
• a quartz glass body is provided, preferably a quartz glass body produced according to method 100.
• Such a quartz glass body may be a solid or a hollow quartz glass body.
• a shaped body is formed in a second step 1602.
• the fictive temperature is determined by means of Raman spectroscopy on the basis of the Raman scattering intensity at about 606 cm -1
• the procedure and evaluation is described in the article by Pfleiderer et al., The UV-induced 210 nm absorption band in fused silica with different thermal history and stoichiometry. ; Journal of Non ⁇
• the OH content of the glass is determined by infrared spectroscopy.
• the method "Optical Determinations of OH in Fused Silica” (J.A.P., 37, 3991 (1966)), as reported by D.M. Dodd & D.M. Fraser, is used instead of the apparatus described therein, an FTIR spectrometer (Fourier transform).
• REPORTED SHEET (RULE 91) ISA / EP Infrared spectrometer, currently System 2000 from Perkin Elmer).
• the evaluation of the spectra can be carried out in principle both at the absorption band at about 3670 cm-1 and at the absorption band at about 7200 cm-1.
• the selection of the band used is based on the rule that the transmission loss due to the OH absorption is between 10 and 90%.
• Oxygen Deficiency Centers ODCs
• ODC (I) absorption at 165 nm is determined by means of a transmission measurement on a 1-2 mm thick sample using a vacuum UV spectrometer, model VUVAS 2000, from McPherson, Inc. (USA).
• N defect concentration [1 / cm 3 ]
• OES or MS depends on the expected element concentration. Typical determination limits for the MS are lppb, for the OES lOppb (in each case based on the weighted sample amount).
• the determination of the element concentration with the measuring instruments is carried out in accordance with the equipment manufacturers (ICP-MS: Agilent 7500ce, ICP-OES: Perkin Elmer 7300 DV) and using certified reference liquids for calibration.
• the element concentration in the solution (15 ml) determined by the devices is then converted to the original sample weight (2 g).
• a well-defined volume of the liquid is weighed into a measuring vessel which is inert with respect to the liquid and its constituents, the empty weight and the weight of the filled vessel being measured.
• the density results from the difference between the two weight measurements divided by the volume of liquid introduced.
• the measuring solution has a pH in the range between 5 and 7.
• the determination of the chloride content of the measuring solution is carried out by means of ion-sensitive (chloride) electrode, suitable for the expected concentration range, and display device according to the manufacturer's instructions here a type Cl-500 electrode and reference electrode type R-503 / D on a pMX 3000 / pH / ION the company Scientific-Technical Workshops GmbH.
• chloride ion-sensitive
• Chlorine contents ⁇ 50 ppm up to 0.1 ppm in quartz glass are determined by neutron activation analysis (NAA).
• NAA neutron activation analysis
• 3 drill bits each with a diameter of 3 mm and a length of 1 cm each are drawn from the quartz glass body to be examined.
• quartz glass samples The transmission of quartz glass samples is determined using commercial grid or FTIR spectrometers from Perkin Elmer (Lambda 900 [190-3000nm] or System 2000 [1000-5000nm]). The choice depends on the required measuring range.
• the specimens are polished in a plane-parallel manner (surface roughness RMS ⁇ 0.5 nm) and the surface after polishing is freed of all residues by ultrasonic treatment.
• the sample thickness is 1cm.
• a thicker or thinner sample can also be selected to remain within the instrument's measuring range. It becomes a sample thickness (measuring length) selected, in which due to the beam passage through the sample only slightly artifacts occur and at the same time a sufficiently detectable effect is measured.
• the sample is placed in front of an Ulbrich sphere in the beam path.
• the refractive index distribution of tubes / rods can be determined by means of a York Technology Ltd. Preform Profiler PI 02 or PI 04.
• the rod is placed horizontally in the measuring chamber and this sealed. Thereafter, the measuring chamber is filled up with an immersion oil having a refractive index at the test wavelength of 633nm, which is very similar to that of the outermost glass layer at 633nm.
• the laser beam then passes through the measuring chamber. Behind the measuring chamber (in beam direction) a detector is mounted, which determines the deflection angle (jet entry in opposite to jet exit from the measuring chamber).
• the diametric refractive index profile can be reconstructed by means of an inverse Abel transformation.
• the refractive index of a sample is analogous to the above description with the York Technology Ltd. Preform Profiler PI 04 determined. In the case of isotropic samples, only one value is obtained even when measuring the refractive index distribution, the refractive index.
• the quantitative determination of the surface carbon content of silica granules and silica powder is carried out on a carbon analyzer RC612 from Leco Corporation, USA, by the complete oxidation of all surface carbon contaminants (except SiC) with oxygen to carbon dioxide.
• a carbon analyzer RC612 from Leco Corporation, USA
• 4.0 g of a sample are weighed and introduced into the carbon analyzer in a quartz glass boat.
• the sample is lapped with pure oxygen and heated to 900 ° C for 180 seconds.
• the resulting C0 2 is detected by the infrared detector of the carbon analyzer. Under these measurement conditions, the detection limit is ⁇ 1 ppm (ppm by weight) carbon.
• quartz glass boat is available as a consumable for LECO analyzer with the LECO number 781-335 in the laboratory supplies trade, in the present case of Deslis laboratory trade, Flur No 21, D-40235 Dusseldorf (Germany), Deslis- No. LQ-130XL.
• Such a boat has the dimensions of width / length / height of about 25mm / 60mm / 15mm.
• the quartz glass boat is filled halfway up with sample material. For silicon dioxide powder, a weight of 1.0 g of sample material can be achieved in this way. The lower detection limit is then ⁇ 1 ppm by weight of carbon.
• a weight of 4 g of a silica granules is reached (average particle size in the range of 100 to 500 ⁇ ).
• the lower detection limit is then about 0.1 ppm by weight of carbon.
• the Curl parameter (also called: “Fiber Curl”) is determined in accordance with DIN EN 60793-1-34: 2007-01 (German version of the standard IEC 60793-1-34: 2006) in the sections A.2.1, A.3.2 and A.4.1 ("extrema technique").
• the slurry is adjusted to a concentration of 30% solids by weight with demineralized water (Direct-Q 3UV, Millipore, water grade: 18.2 MQcm).
• demineralized water Direct-Q 3UV, Millipore, water grade: 18.2 MQcm.
• the viscosity is then measured on an MCR102 of the Anton Paar company. For this purpose, the viscosity is measured at 5 revolutions / minute (rpm). It is measured at a temperature of 23 ° C and an air pressure of 1013 hPa.
• the slurry is adjusted to a concentration of 30% solids by weight with demineralized water (Direct-Q 3UV, Millipore, water grade: 18.2 MQcm).
• demineralized water Direct-Q 3UV, Millipore, water grade: 18.2 MQcm.
• the thixotropy is determined with a MCR102 of the Fa. Anton pair with a cone-plate arrangement.
• the viscosity is measured at 5 and at 50 revolutions / minute (rpm).
• the quotient of the first and the second value gives the thixotropic index.
• the measurement is measured at a temperature of 23 ° C.
• a zeta potential measuring cell (Flow Cell, Beckman Coulter) is used.
• the sample is dissolved in demineralized water (Direct-Q 3UV, Millipore, water quality: 18.2 MQcm) to obtain a 20 mL solution at 1 g / L concentration.
• the pH is brought to 7 by addition of HNO 3 solutions having the concentrations of 0.1 mol / L and 1 mol / L and a NaOH solution having the concentration of 0.1 mol / L. It is measured at a temperature of 23 ° C.
• the isoelectric point a zeta potential measuring cell (Flow Cell, Beckman Coulter) and an autotitrator (DelsaNano AT, Beckman Coulter) are used.
• the sample is dissolved in demineralized water (Direct-Q 3UV, Millipore, water quality: 18.2 MQcm) to obtain a 20 mL solution at 1 g / L concentration.
• the pH is varied by adding HNO 3 solutions having the concentrations of 0.1 mol / L and 1 mol / L and a NaOH solution having the concentration of 0.1 mol / L.
• the isoelectric point is the pH at which the zeta potential is zero. It is measured at a temperature of 23 ° C. pH of the slurry
• the pH of the slurry is measured by means of a WTW 3210 from the companyticianlich-Technische-Werk Toon GmbH.
• the electrode used is the pH 3210 Set 3 from WTW. It is measured at a temperature of 23 ° C.
• the bulk density is determined according to the standard DIN ISO 697: 1984-01 with a SMG 697 from Powtec.
• the bulk material (silica powder or granules) does not form lumps.
• the tamped density is measured according to DIN ISO 787: 1995-10. v. Determination of the pore size distribution
• the pore size distribution is determined according to DIN 66133 (with a surface tension of 480 mN / m and a contact angle of 140 °).
• Pascal 400 from Porotec is used.
• pore sizes from 3.7 nm to 100 ⁇ Pascal 140 is used by the company. Porotec.
• the sample is subjected to a pressure treatment before the measurement.
• a Manual Hydraulic Press (Order No. 15011 from Specac Ltd., River House, 97 Cray Avenue, Orpington, Kent BR5 4HE, U.K.) is used.
• sample material 250 mg are weighed into a "pellet die" with a 13 mm inner diameter from Specac Ltd. and loaded with 1 t as indicated.This load is held for 5 s and readjusted if necessary, then the sample is decompressed and allowed to stand for 4 h 105 ⁇ 2 ° C dried in a convection oven.
• the sample is weighed into the Type 10 penetrometer to a precision of 0.001 g and, for a good reproducibility of the measurement, is chosen so that the stem volume used, ie the percentage of Hg volume consumed to fill the penetrometer, ranges between 20%.
• the penetrometer is then slowly evacuated to 50 ⁇ Hg and kept at this temperature for 5 min
• the primary particle size is measured by means of a scanning electron microscope (SEM) model Zeiss Ultra 55.
• SEM scanning electron microscope
• the sample is suspended in demineralized water (Direct-Q 3UV, Millipore, water quality: 18.2 MQcm) to obtain an extremely dilute suspension.
• the suspension is treated with the ultrasonic probe (UW 2070, Bandelin electronic, 70 W, 20 kHz) for 1 min and then applied to a carbon adhesive pad.
• UW 2070 Ultrasonic probe
• the mean particle size in suspension is measured by means of a Mastersizer 2000, available from Malvern Instruments Ltd., UK, according to their instruction manual using the laser diffraction method.
• the sample is taken in demineralised water (Direct-Q 3UV, Millipore, water quality: 18.2
• the particle size and grain size of the solid are determined using a Camsizers XT available from Retsch
• the tare weight of the measuring cells used (clean and dry) is weighed.
• the type of measuring cell is chosen so that the supplied sample material and the filling rod fill the measuring cell as much as possible and the dead space is reduced to a minimum.
• the sample material is brought into the measuring cell.
• the amount of sample material is selected so that the expected reading is 10-20 m 2 / g.
• the measuring cells are in the
• the viscosity of the glass is determined by means of the beam bending viscometer type 401 - TA Instruments with the manufacturer software WinTA (currently version 9.0) under Windows 10 according to the standard DIN ISO 7884-4: 1998-
• the determination of the residual moisture of a sample of silica granules is carried out with the aid of a moisture analyzer HX204 from Mettler Toledo.
• the device works on the principle of thermogravimetry.
• the HX204 is equipped with a halogen heater as heating element.
• the drying temperature is 220 ° C.
• the starting weight of the sample is 10 g ⁇ 10%.
• the measuring method "Standard" is selected and drying is continued until the change in weight does not exceed 1 mg / 140 s Residual moisture results from the difference between the start weight of the sample and the final weight of the sample, divided by the start weight of the sample.
• the aerosol generated from the atomization of a siloxane with air (A) is introduced under pressure into a flame, which by ignition of a mixture of oxygen-enriched air (B) and
• OMCTS octamethylcyclotetrasiloxane
• SiC silicon tetrachloride
• a particle stream of silica powder is introduced over the top of a standing column. Water vapor at a temperature (A) and air is supplied via the foot of the column. The column is held by an internal heater to a temperature (B) at the column head and a second temperature (C) at the column base. After leaving the column (residence time (D)), the silica powder has in particular the properties shown in Table 6. The process parameters are given in Table 5.
• the silica powders obtained in Examples C-1 and C-2 each have a low chlorine content and a moderate pH in suspension.
• the carbon content of Example C-2 is higher than C-1.
• a particle stream of silica powder is introduced over the top of a standing column. About the foot of the column, a neutralizing agent and air is supplied. The column is held by an internal heater to a temperature (B) at the column head and a second temperature (C) at the column base. After leaving the column (residence time (D)), the silica powder has in particular the properties shown in Table 8. The process parameters are given in Table 7. Table 7
• silica granules from silica powder
• a silica powder is dispersed in deionized water.
• An intensive mixer Type R of the Maschinenfabrik Gustav Eirich is used.
• the resulting suspensions are conveyed through a membrane pump and thereby pressurized and transferred through a nozzle into droplets. These are dried in a spray tower and collect on the bottom.
• the process parameters are given in Table 9, the properties of the resulting granules in Table 10.
• Experimental data for this example are marked El-x. In E2-21 to E2-23, aluminum oxide is added as an additive. In E2-31 and E2-32
• Installation height distance between the nozzle and the lowest point of the spray tower interior in the direction of the
• Aeroxide Alu 65 fumed fumed alumina, particle size 65 ⁇ (Evonik Industries AG, Essen (Germany)
• the granules are all porous, show a uniform and spherical shape (all microscopic examination.) They do not tend to caking or sticking.
• Silica granules are first treated with oxygen in a rotary kiln, optionally at a temperature T1. Subsequently, the silica granules are treated in cocurrent with chlorine-containing components, wherein the temperature is increased to a temperature T2.
• the process parameters are given in Table 11, the properties of the resulting treated granules in Table 12 .. Table 11
• the throughput was chosen as the control variable. This means that during operation the mass flow emerging from the rotary kiln is weighed and then the rotational speed and / or the inclination of the rotary kiln are adjusted accordingly. For example, an increase in throughput can be achieved by a) increasing the
• Rotational speed or b) increasing the inclination of the rotary tube from the horizontal, or a combination of a) and b).
• the granules after the purification step show a significantly reduced carbon content (such as low-carbon granules, eg Fl-1) and a significantly lower content of alkaline earth metals. SiC formation was not observed. Forming a vitreous body
• Silica granules according to line 2 of Table 13 were used as the raw material.
• a graphite mold having an annular cavity and an outer diameter of the molded article of d a , an inner diameter of the molded article of d t and a length / was prepared.
• a high-purity graphite foil having a thickness of 1 mm was applied to the inner wall of the outer molded body, and a graphite foil of the same high-purity graphite having a thickness of 1 mm was applied to the outer wall of the inner molded body.
• a high-purity graphite sheet of a high-purity graphite having a bulk density of 1.2 g / cm 3 and a thickness of 0.4 mm was applied to the bottom of the annular cavity of the mold (in G-2: cylindrical cavity).
• the high-purity graphite mold provided with the graphite foil was filled with the silica granules.
• the filled graphite mold is placed in an oven and this is pressurized with vacuum.
• the filled silica granules were brought from the temperature Tl at a heating rate Rl to a temperature T2 and maintained for the time t2 on this.
• the heating rate R2 was heated to T3, then brought to the temperature T4 without further annealing at the heating rate R3, further to the temperature T5 at the heating rate R4, and maintained at the temperature T5 for the time t5.
• the furnace is pressurized with 1.6 * 10 6 Pa nitrogen.
• the mold was gradually cooled.
• the mold was gradually cooled further to T6.
• Table 13 the properties of the quartz glass body formed in Table 14. "Gradual cooling" means that the mold is left without cooling measures in the oven is switched off, so cool only by releasing the heat to the environment.
• the quartz glass body previously prepared in Example G2-1 is glass-blown into a bell. This forms, together with a lid (also made of quartz glass, including feedthroughs) a reaction chamber into which silicon wafers for semiconductor production are introduced and subsequently subjected to specific processes.
• the reaction chamber formed from the quartz glass produced according to Example G showed a significantly longer operating time (at comparable temperature conditions) than a conventional one. In addition, a better dimensional stability at high temperatures was observed. J. Making a large pipe
• Example Gl-1 and G2-x were thermoformed in two steps at a temperature of 2100 ° C. Fluctuations in homogeneity of substance in such treatment lead to variations in the geometry of the reshaped vitreous body.
• the general procedure for such a two-stage forming step is known and described for example in DE 10 2013 107 434 AI, paragraph [0051] - [0065].
• the glass body of Example Gl-1 and G2-x is referred to there as a hollow cylinder.
• the properties of the glass body of Example Jl-1 and J2-x formed in a first step are given in Table 17, the properties after the second forming step in Table 18.
• the test specimen (glass tube) is measured on a glass lathe. For this purpose, the specimen does not rotate.
• An optical measuring head is moved along the test body parallel to the longitudinal axis of the test body and the wall thickness is continuously recorded as the distance of the measuring head from the outer surface of the test body and recorded by data technology.
• the measuring head used was a CHRocodile M4 from Precitec High Resolution.

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